Polyethylene composition and film having outstanding properties

ABSTRACT

A polyethylene composition including a first polyethylene which is an ethylene copolymer having a weight average molecular weight of from 70,000 to 250,000 and a molecular weight distribution M w /M n  of &lt;2.3, a second polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of from 50,000 to 200,000 and a molecular weight distribution M w /M n  of &lt;2.3, and a third polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of from 70,000 to 200,000 and a molecular weight distribution M w /M n  of &lt;2.3, where the first polyethylene has more short chain branching than the second polyethylene or the third polyethylene.

CROSS REFERENCE TO RELATED APPLICAITONS

This application is a continuation of U.S. patent application Ser. No.16/507,477, filed on Jul. 10, 2019, which claims the benefit of theearlier filing date of Canadian application serial number 3011031 filedon Jul. 11, 2018, the contents of both of which are incorporated hereinby reference in their entirety.

TECHNICAL FIELD

The present disclosure provides polyethylene compositions which whenblown into film have good stiffness, good permeability, good dart andtear properties and remarkable sealability. The polyethylenecompositions include three different polyethylene components, each ofwhich are made with a single site polymerization catalyst.

BACKGROUND

Multicomponent polyethylene compositions are well known in the art. Onemethod to access multicomponent polyethylene compositions is to use twoor more distinct polymerization catalysts in one or more polymerizationreactors. For example, the use of single site and Ziegler-Natta typepolymerization catalysts in at least two distinct solutionpolymerization reactors is known. Such reactors may be configured inseries or in parallel.

Solution polymerization processes are generally carried out attemperatures above the melting point of the ethylene homopolymer orcopolymer product being made. In a typical solution polymerizationprocess, catalyst components, solvent, monomers and hydrogen are fedunder pressure to one or more reactors.

For solution phase ethylene polymerization, or ethylenecopolymerization, reactor temperatures can range from about 80° C. toabout 300° C. while pressures generally range from about 3 megapascalgauge (MPag) to about 45 MPag. The ethylene homopolymer or copolymerproduced remains dissolved in the solvent under reactor conditions. Theresidence time of the solvent in the reactor is relatively short, forexample, from about 1 second to about 20 minutes. The solution processcan be operated under a wide range of process conditions that allow theproduction of a wide variety of ethylene polymers. Post reactor, thepolymerization reaction is quenched to prevent further polymerization,by adding a catalyst deactivator, and optionally passivated, by addingan acid scavenger. Once deactivated (and optionally passivated), thepolymer solution is passed to a polymer recovery operation (adevolatilization system) where the ethylene homopolymer or copolymer isseparated from process solvent, unreacted residual ethylene andunreacted optional α-olefin(s).

Regardless of the manner of production, there remains a need to improvethe performance of multicomponent polyethylene compositions in filmapplications.

SUMMARY

The present disclosure provides polyethylene compositions which whenmade into film have a good balance of stiffness, dart impact strength,tear strength, permeability and sealing properties.

An embodiment of the disclosure is a polyethylene composition including:

from 15 to 80 wt % of a first polyethylene which is an ethylenecopolymer, the first polyethylene having a weight average molecularweight, Mw, of from 70,000 to 250,000, a molecular weight distribution,M_(w)/M_(n), of <2.3 and from 5 to 100 short chain branches per thousandcarbon atoms;

from 5 to 50 wt % of a second polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight, Mw, of from 50,000 to 200,000, amolecular weight distribution, M_(w)/M_(n), of <2.3 and from 0 to 15short chain branches per thousand carbon atoms; and

from 5 to 50 wt % of a third polyethylene which is an ethylene copolymeror an ethylene homopolymer, the third polyethylene having a weightaverage molecular weight, Mw, of from 70,000 to 200,000, a molecularweight distribution, M_(w)/M_(n), of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms;

wherein the number of short chain branches per thousand carbon atoms inthe first polyethylene (SCB_(PE-1)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)) and the third polyethylene (SCB_(PE-3)); and thepolyethylene composition has a density of ≤0.939 g/cm³, a melt index I₂of from 0.1 to 10 g/10 min, and a composition distribution breadth indexCDBI₅₀ obtained from a crystallization elution fractionation (CEF)analysis of <45 wt %.

An embodiment of the disclosure is a film layer having a thickness offrom 0.5 to 10 mil, including a polyethylene composition including:

from 15 to 80 wt % of a first polyethylene which is an ethylenecopolymer, the first polyethylene having a weight average molecularweight, Mw, of from 70,000 to 250,000, a molecular weight distribution,M_(w)/M_(n), of <2.3 and from 5 to 100 short chain branches per thousandcarbon atoms;

from 5 to 50 wt % of a second polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight, Mw, of from 50,000 to 200,000, amolecular weight distribution, M_(w)/M_(n), of <2.3 and from 0 to 15short chain branches per thousand carbon atoms; and

from 5 to 50 wt % of a third polyethylene which is an ethylene copolymeror an ethylene homopolymer, the third polyethylene having a weightaverage molecular weight, Mw, of from 70,000 to 200,000, a molecularweight distribution, M_(w)/M_(n), of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms;

wherein the number of short chain branches per thousand carbon atoms inthe first polyethylene (SCB_(PE-1)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)) and the third polyethylene (SCB_(PE-3)); and thepolyethylene composition has a density of 0.939 g/cm³, a melt index I₂of from 0.1 to 10 g/10 min, and a composition distribution breadth indexCDBI₅₀ obtained from a crystallization elution fractionation (CEF)analysis of <45 wt %.

In an embodiment, a film layer has a dart impact strength of ≥400 g/mil.

In an embodiment, a film layer has a machine direction (MD) tearstrength of ≥400 g/mil.

In an embodiment, a film layer has a machine direction (MD) 1% secantmodulus of ≥200 MPa when measured at a film thickness of about 1 mil.

In an embodiment, a film layer has a seal initiation temperature (SIT)of ≤85° C. when measured at a film thickness of about 2 mil.

In an embodiment, the film layer has an area of hot tack window (AHTW)of ≥220 Newtons·° C. when measured at a film thickness of about 2 mil.

In an embodiment, the film layer has an oxygen transmission rate (OTR)of ≥600 cm³ per 100 inch² when measured at a film thickness of about 1mil.

In an embodiment, the film layer has an oxygen transmission rate (OTR)of ≥600 cm³ per 100 inch² when measured at a film thickness of about 1mil.

An embodiment of the disclosure is a film layer having a thickness offrom 0.5 to 10 mil, wherein the film layer has a has a machine direction(MD) 1% secant modulus of ≥200 MPa when measured at a film thickness ofabout 1 mil, an oxygen transmission rate (OTR) of ≥600 cm³ per 100 inch²when measured at a film thickness of about 1 mil, a seal initiationtemperature (SIT) of ≤85° C. when measured at a film thickness of about2 mil, an area of hot tack window (AHTW) of ≥220 Newtons·° C. whenmeasured at a film thickness of about 2 mil, a dart impact strength of≥400 g/mil and a machine direction (MD) tear strength of ≥400 g/mil.

An embodiment of the disclosure is a film layer having a thickness offrom 0.5 to 10 mil, wherein the film layer satisfies at least one of thefollowing relationships:

i) area of hot tack window (AHTW)>−2.0981 (machine direction (MD) 1%secant modulus)+564.28;

wherein the AHTW is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil;

ii) oxygen transmission rate (OTR)>−5.4297 (machine direction (MD) 1%secant modulus)+1767.8;

wherein the OTR is measured at a film thickness of about 1 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil; and

iii) seal initiation temperature (SIT)<0.366 (machine direction (MD) 1%secant modulus)+22.509.

wherein the SIT is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

An embodiment of the disclosure is a film layer having a thickness offrom 0.5 to 10 mil, wherein the film layer satisfies each of thefollowing relationships:

i) area of hot tack window (AHTW)>−2.0981 (machine direction (MD) 1%secant modulus)+564.28;

wherein the AHTW is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil;

ii) oxygen transmission rate (OTR)−5.4297 (machine direction (MD) 1%secant modulus)+1767.8;

wherein the OTR is measured at a film thickness of about 1 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil; and

iii) seal initiation temperature (SIT)<0.366 (machine direction (MD) 1%secant modulus)+22.509;

wherein the SIT is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the gel permeation chromatographs (GPC) with refractiveindex detection of a polyethylene composition made according to thepresent disclosure as well as for some comparative polyethylenes.

FIG. 2 shows the gel permeation chromatographs with Fourier transforminfra-red (GPC-FTIR) detection obtained for a polyethylene compositionmade according to the present disclosure as well as for some comparativepolyethylenes. The comonomer content, shown as the number of short chainbranches per 1000 carbons (y-axis), is given relative to the copolymermolecular weight (x-axis). The upwardly sloping line (from left toright) is the short chain branching (in short chain branches per 1000carbons atoms) determined by FTIR. As can be seen in the Figure, forInventive Example 1, the number of short chain branches initiallyincreases at higher molecular weights and then decreases again at stillhigher molecular weights, and hence the comonomer incorporation is saidto be “partially reversed” with a peak or maximum present.

FIG. 3 shows the differential scanning calorimetry analysis (DSC) andprofile of a polyethylene composition made according to the presentdisclosure as well as for some comparative polyethylenes.

FIG. 4 shows the hot tack profiles for film made using a polyethylenecomposition made according to the present disclosure as well as thosefor several comparative polyethylenes.

FIG. 5 shows the cold seal profiles for film made using a polyethylenecomposition made according to the present disclosure as well as thosefor several comparative polyethylenes.

FIG. 6 shows a plot of the equation: AHTW=−2.0981 (machine direction(MD) 1% secant modulus)+564.28. The values for the AHTW (the y-axis) areplotted against the corresponding machine direction (MD) 1% secantmodulus values (the x-axis) for film made from a polyethylenecomposition of the present disclosure as well as those for film madefrom several comparative polyethylenes.

FIG. 7 shows a plot of the equation: SIT=0.366 (machine direction (MD)1% secant modulus)+22.509. The values for the SIT (the y-axis) areplotted against the corresponding machine direction (MD) 1% secantmodulus values (the x-axis) for film made from a polyethylenecomposition of the present disclosure as well as those for film madefrom several comparative polyethylenes.

FIG. 8 shows a plot of the equation: OTR=−5.4297 (machine direction (MD)1% secant modulus)+1767.8. The values for the OTR (the y-axis) areplotted against the corresponding machine direction (MD) 1% secantmodulus values (the x-axis) for film made from a polyethylenecomposition of the present disclosure as well as those for film madefrom several comparative polyethylenes. “1/2.5 film” means that the filmwas made at 1 mil of thickness with a blow up ratio (BUR) of 2.5.

DETAILED DESCRIPTION Definition of Terms

Other than in the examples or where otherwise indicated, all numbers orexpressions referring to quantities of ingredients, extrusionconditions, etc., used in the specification and claims are to beunderstood as modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the desired properties thatthe various embodiments desire to obtain. At the very least, and not asan attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. The numerical values set forth inthe specific examples are reported as precisely as possible. Anynumerical values, however, inherently contain certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements.

It should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

In order to form a more complete understanding of this disclosure thefollowing terms are defined and should be used with the accompanyingfigures and the description of the various embodiments throughout.

As used herein, the term “monomer” refers to a small molecule that maychemically react and become chemically bonded with itself or othermonomers to form a polymer.

As used herein, the term “α-olefin” or “alpha-olefin” is used todescribe a monomer having a linear hydrocarbon chain containing from 3to 20 carbon atoms having a double bond at one end of the chain; anequivalent term is “linear α-olefin”.

As used herein, the term “polyethylene” or “ethylene polymer”, refers tomacromolecules produced from ethylene monomers and optionally one ormore additional monomers; regardless of the specific catalyst orspecific process used to make the ethylene polymer. In the polyethyleneart, the one or more additional monomers are called “comonomer(s)” andoften include α-olefins. The term “homopolymer” refers to a polymer thatcontains only one type of monomer. An “ethylene homopolymer” is madeusing only ethylene as a polymerizable monomer. The term “copolymer”refers to a polymer that contains two or more types of monomer. An“ethylene copolymer” is made using ethylene and one or more other typesof polymerizable monomer. Common polyethylenes include high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE), very low density polyethylene (VLDPE),ultralow density polyethylene (ULDPE), plastomer and elastomers. Theterm polyethylene also includes polyethylene terpolymers which mayinclude two or more comonomers in addition to ethylene. The termpolyethylene also includes combinations of, or blends of, thepolyethylenes described above.

The term “heterogeneously branched polyethylene” refers to a subset ofpolymers in the ethylene polymer group that are produced using aheterogeneous catalyst system; non-limiting examples of which includeZiegler-Natta or chromium catalysts, both of which are well known in theart.

The term “homogeneously branched polyethylene” refers to a subset ofpolymers in the ethylene polymer group that are produced usingsingle-site catalysts; non-limiting examples of which includemetallocene catalysts, phosphinimine catalysts, and constrained geometrycatalysts all of which are well known in the art.

Typically, homogeneously branched polyethylenes have narrow molecularweight distributions, for example gel permeation chromatography (GPC)M_(w)/M_(n) values of less than 2.8, especially less than about 2.3,although exceptions may arise; M_(w) and M_(n) refer to weight andnumber average molecular weights, respectively. In contrast, theM_(w)/M_(n) of heterogeneously branched ethylene polymers are typicallygreater than the M_(w)/M_(n) of homogeneous polyethylene. In general,homogeneously branched ethylene polymers also have a narrow comonomerdistribution, i.e. each macromolecule within the molecular weightdistribution has a similar comonomer content. Frequently, thecomposition distribution breadth index “CDBI” is used to quantify howthe comonomer is distributed within an ethylene polymer, as well as todifferentiate ethylene polymers produced with different catalysts orprocesses. The “CDBI₅₀” is defined as the percent of ethylene polymerwhose composition is within 50 weight percent (wt %) of the mediancomonomer composition; this definition is consistent with that describedin WO 93/03093 assigned to Exxon Chemical Patents Inc. The CDBI₅₀ of anethylene interpolymer can be calculated from TREF curves (TemperatureRising Elution Fractionation); the TREF method is described in Wild, etal., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455.Typically the CDBI₅₀ of homogeneously branched ethylene polymers aregreater than about 70% or greater than about 75%. In contrast, theCDBI₅₀ of α-olefin containing heterogeneously branched ethylene polymersare generally lower than the CDBI₅₀ of homogeneous ethylene polymers.For example, the CDBI₅₀ of a heterogeneously branched ethylene polymermay be less than about 75%, or less than about 70%.

It is well known to those skilled in the art, that homogeneouslybranched ethylene polymers are frequently further subdivided into“linear homogeneous ethylene polymers” and “substantially linearhomogeneous ethylene polymers”. These two subgroups differ in the amountof long chain branching: more specifically, linear homogeneous ethylenepolymers have less than about 0.01 long chain branches per 1000 carbonatoms; while substantially linear ethylene polymers have greater thanabout 0.01 to about 3.0 long chain branches per 1000 carbon atoms. Along chain branch is macromolecular in nature, i.e. similar in length tothe macromolecule that the long chain branch is attached to. Hereafter,in this disclosure, the term “homogeneously branched polyethylene” or“homogeneously branched ethylene polymer” refers to both linearhomogeneous ethylene polymers and substantially linear homogeneousethylene polymers.

The term “thermoplastic” refers to a polymer that becomes liquid whenheated, will flow under pressure and solidify when cooled. Thermoplasticpolymers include ethylene polymers as well as other polymers used in theplastic industry; non-limiting examples of other polymers commonly usedin film applications include barrier resins (EVOH), tie resins,polyethylene terephthalate (PET), polyamides and the like.

As used herein the term “monolayer film” refers to a film containing asingle layer of one or more thermoplastics.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or“hydrocarbyl group” refers to linear or cyclic, aliphatic, olefinic,acetylenic and aryl (aromatic) radicals including hydrogen and carbonthat are deficient by one hydrogen.

As used herein, an “alkyl radical” includes linear, branched and cyclicparaffin radicals that are deficient by one hydrogen radical;non-limiting examples include methyl (—CH₃) and ethyl (—CH₂CH₃)radicals. The term “alkenyl radical” refers to linear, branched andcyclic hydrocarbons containing at least one carbon-carbon double bondthat is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyland other radicals whose molecules have an aromatic ring structure;non-limiting examples include naphthylene, phenanthrene and anthracene.An “arylalkyl” group is an alkyl group having an aryl group pendantthere from; non-limiting examples include benzyl, phenethyl andtolylmethyl; an “alkylaryl” is an aryl group having one or more alkylgroups pendant there from; non-limiting examples include tolyl, xylyl,mesityl and cumyl.

As used herein, the phrase “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon. A“heteroatom-containing group” is a hydrocarbon radical that contains aheteroatom and may contain one or more of the same or differentheteroatoms. In one embodiment, a heteroatom-containing group is ahydrocarbyl group containing from 1 to 3 atoms chosen from boron,aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur.Non-limiting examples of heteroatom-containing groups include radicalsof imines, amines, oxides, phosphines, ethers, ketones, oxoazolinesheterocyclics, oxazolines, thioethers, and the like. The term“heterocyclic” refers to ring systems having a carbon backbone thatinclude from 1 to 3 atoms chosen from boron, aluminum, silicon,germanium, nitrogen, phosphorous, oxygen and sulfur.

As used herein the term “unsubstituted” means that hydrogen radicals arebounded to the molecular group that follows the term unsubstituted. Theterm “substituted” means that the group following this term possessesone or more moieties that have replaced one or more hydrogen radicals inany position within the group; non-limiting examples of moieties includehalogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxylgroups, amine groups, phosphine groups, alkoxy groups, phenyl groups,naphthyl groups, C₁ to C₃₀ alkyl groups, C₂ to C₃₀ alkenyl groups, andcombinations thereof. Non-limiting examples of substituted alkyls andaryls include: acyl radicals, alkylamino radicals, alkoxy radicals,aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals,alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, arylamino radicals and combinations thereof.

In the present disclosure, a polyethylene composition will include atleast the following types of polymers: a first polyethylene which is anethylene copolymer and which has a Mw/Mn of less than about 2.3; asecond polyethylene which is an ethylene copolymer or an ethylenehomopolymer which is different from the first polyethylene and which hasa Mw/Mn of less than about 2.3; and a third polyethylene which isdifferent from the first polyethylene and the second polyethylene andwhich is an ethylene copolymer or an ethylene homopolymer which has aMw/Mn of less than about 2.3. Each of these polyethylene components, andthe polyethylene composition of which they are each a part are furtherdescribed below.

The First Polyethylene

In an embodiment of the disclosure, the first polyethylene is made witha single site catalyst, non-limiting examples of which includephosphinimine catalysts, metallocene catalysts, and constrained geometrycatalysts, all of which are well known in the art.

In an embodiment of the disclosure, the first polyethylene is anethylene copolymer. Suitable alpha-olefins which may be copolymerizedwith ethylene to make an ethylene copolymer include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene.

In an embodiment of the disclosure, the first polyethylene is ahomogeneously branched ethylene copolymer.

In an embodiment of the disclosure, the first polyethylene is anethylene/1-octene copolymer.

In an embodiment of the disclosure, the first polyethylene is made witha phosphinimine catalyst.

In an embodiment of the disclosure, a phosphinimine catalyst isrepresented by the formula:

(L^(A))_(a)M(Pl)_(b)(Q)_(n)

wherein (L^(A)) represents is cyclopentadienyl-type ligand; M representsa metal atom chosen from Ti, Zr, and Hf; Pl represents a phosphinimineligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2;(a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of themetal M.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current disclosure, so long as thefive-carbon ring which bonds to the metal via eta-5 (or in some caseseta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be chosen from aC₁₋₃₀ hydrocarbyl radical (which hydrocarbyl radical may beunsubstituted or further substituted by for example a halide and/or ahydrocarbyl group; for example a suitable substituted C₁₋₃₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical (each of whichmay be further substituted by for example a halide and/or a hydrocarbylgroup); an amido radical which is unsubstituted or substituted by up totwo C₁₋₈ alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; a silyl radical of theformula —Si(R′)₃ wherein each R′ is independently chosen from hydrogen,a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ aryl or aryloxy radicals; and agermanyl radical of the formula —Ge(R′)₃ wherein R′ is as defineddirectly above.

The phosphinimine ligand, Pl, is defined by the formula:

(R^(p))₃═N—

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R⁵)₃, wherein the RS groups are independentlyselected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxy radical, a C₆₋₁₀aryl radical, a C₆₋₁₀ aryloxy radical, or a germanyl radical of formula—Ge(R^(G))₃, wherein the R^(G) groups are defined as R^(s) is defined inthis paragraph.

In an embodiment of the disclosure, the metal, M in the phosphiniminecatalyst is titanium, Ti.

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene is cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)₃PN)TiCl₂.

In an embodiment of the disclosure, the first polyethylene is made witha metallocene catalyst.

In an embodiment of the disclosure, the first polyethylene is made witha bridged metallocene catalyst.

In an embodiment of the disclosure, the first polyethylene is made witha bridged metallocene catalyst having the formula I:

In Formula (I): M is a group 4 metal selected from titanium, zirconiumor hafnium; G is a group 14 element selected from carbon, silicon,germanium, tin or lead; R₁ is a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₂ and R₃are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₄ and R₅are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; and Q isindependently an activatable leaving group ligand.

In the current disclosure, the term “activatable,” means that the ligandQ may be cleaved from the metal center M via a protonolysis reaction orabstracted from the metal center M by suitable acidic or electrophiliccatalyst activator compounds (also known as “co-catalyst” compounds)respectively, examples of which are described below. The activatableligand Q may also be transformed into another ligand which is cleaved orabstracted from the metal center M (e.g. a halide may be converted to analkyl group). Without wishing to be bound by any single theory,protonolysis or abstraction reactions generate an active “cationic”metal center which can polymerize olefins.

In embodiments of the present disclosure, the activatable ligand, Q isindependently chosen from a hydrogen atom; a halogen atom; a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, and a C₆₋₁₀ aryl or aryloxyradical, where each of the hydrocarbyl, alkoxy, aryl, or aryl oxideradicals may be un-substituted or further substituted by one or morehalogen or other group; a C₁₋₈ alkyl; a C₁₋₈ alkoxy; a C₆₋₁₀ aryl oraryloxy; an amido or a phosphido radical, but where Q is not acyclopentadienyl. Two Q ligands may also be joined to one another andform for example, a substituted or unsubstituted diene ligand (e.g.1,3-butadiene); or a delocalized heteroatom containing group such as anacetate or acetamidinate group. In a convenient embodiment of thedisclosure, each Q is independently chosen from a halide atom, a C₁₋₄alkyl radical and a benzyl radical. Particularly suitable activatableligands Q are monoanionic such as a halide (e.g. chloride) or ahydrocarbyl (e.g. methyl, benzyl).

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula: [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂].

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂].

In addition to the single site catalyst molecule per se, an activesingle site catalyst system may further include one or more of thefollowing: an alkylaluminoxane co-catalyst and an ionic activator. Thesingle site catalyst system may also optionally include a hinderedphenol.

Although the exact structure of alkylaluminoxane is uncertain, subjectmatter experts generally agree that it is an oligomeric species thatcontain repeating units of the general formula:

(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alkylaluminoxane ismethylaluminoxane (or MAO) wherein each R group is a methyl radical.

In an embodiment of the disclosure, R of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

In an embodiment of the disclosure, the co-catalyst is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneco-catalyst is often used in combination with activatable ligands suchas halogens.

In general, ionic activators are comprised of a cation and a bulkyanion; wherein the latter is substantially non-coordinating.Non-limiting examples of ionic activators are boron ionic activatorsthat are four coordinate with four ligands bonded to the boron atom.Non-limiting examples of boron ionic activators include the followingformulas shown below;

[R⁵]⁺[B(R⁷)₄]⁻

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and

[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ is as defined above.

In both formula, a non-limiting example of R⁷ is a pentafluorophenylradical. In general, boron ionic activators may be described as salts oftetra(perfluorophenyl) boron; non-limiting examples include anilinium,carbonium, oxonium, phosphonium and sulfonium salts oftetra(perfluorophenyl)boron with anilinium and trityl (ortriphenylmethylium). Additional non-limiting examples of ionicactivators include: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

Non-limiting example of hindered phenols include butylated phenolicantioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethylphenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

To produce an active single site catalyst system the quantity and moleratios of the three or four components: the single site catalyst, thealkylaluminoxane, the ionic activator, and the optional hindered phenolare optimized.

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene produces no long chain branches, and thefirst polyethylene will contain no measurable amounts of long chainbranches.

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene produces long chain branches, and the firstpolyethylene will contain long chain branches, hereinafter “LCB”. LCB isa well-known structural phenomenon in polyethylenes and well known tothose of ordinary skill in the art. Traditionally, there are threemethods for LCB analysis, namely, nuclear magnetic resonancespectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci.,Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equippedwith a DRI, a viscometer and a low-angle laser light scatteringdetector, for example see W. W. Yau and D. R. Hill, Int. J. Polym. Anal.Charact. 1996; 2:151; and rheology, for example see W. W. Graessley,Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long chainbranch is macromolecular in nature, i.e. long enough to be seen in anNMR spectra, triple detector SEC experiments or rheological experiments.

In embodiments of the disclosure, the upper limit on the molecularweight distribution, M_(w)/M_(n) of the first polyethylene may be about2.8, or about 2.5, or about 2.4, or about 2.3, or about 2.2. Inembodiments of the disclosure, the lower limit on the molecular weightdistribution, M_(w)/M_(n) of the first polyethylene may be about 1.4, orabout 1.6, or about 1.7, or about 1.8, or about 1.9.

In embodiments of the disclosure, the first polyethylene has a molecularweight distribution, M_(w)/M_(n) of <2.3, or <2.1, or <2.0 or about 2.0.In embodiments of the disclosure, the first polyethylene has a molecularweight distribution, M_(w)/M_(n) of from about 1.7 to about 2.2.

In an embodiment of the disclosure, the first polyethylene has from 1 to200 short chain branches per thousand carbon atoms (SCB_(PE-1)). Infurther embodiments, the first polyethylene has from 3 to 150 shortchain branches per thousand carbon atoms (SCB_(PE-1)), or from 5 to 100short chain branches per thousand carbon atoms (SCB_(PE-1)), or from 10to 100 short chain branches per thousand carbon atoms (SCB_(PE-1)), orfrom 5 to 75 short chain branches per thousand carbon atoms(SCB_(PE-1)), or from 10 to 75 short chain branches per thousand carbonatoms (SCB_(PE-1)), or from 15 to 75 short chain branches per thousandcarbon atoms (SCB_(PE-1)), or from 20 to 75 short chain branches perthousand carbon atoms (SCB_(PE-1)). In still further embodiments, thefirst polyethylene has from 15 to 60 short chain branches per thousandcarbon atoms (SCB_(PE-1)), or from 15 to 60 short chain branches perthousand carbon atoms (SCB_(PE-1)), or from 20 to 50 short chainbranches per thousand carbon atoms (SCB_(PE-1)), or from 25 to 60 shortchain branches per thousand carbon atoms (SCB_(PE-1)), or from 15 to 50short chain branches per thousand carbon atoms (SCB_(PE-1)), or from 20to 50 short chain branches per thousand carbon atoms (SCB_(PE-1)).

The short chain branching (i.e. the short chain branching per thousandcarbons, SCB_(PE-1)) is the branching due to the presence of analpha-olefin comonomer in the polyethylene and will for example have twocarbon atoms for a 1-butene comonomer, or four carbon atoms for a1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in the second polyethylene (SCB_(PE-2)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in the third polyethylene (SCB_(PE-3)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in each of the second polyethylene (SCB_(PE-2)) and the thirdpolyethylene (SCB_(PE-3)).

In embodiments of the disclosure, the upper limit on the density, d1 ofthe first polyethylene may be about 0.975 g/cm³; in some cases about0.965 g/cm³ and; in other cases about 0.955 g/cm³. In embodiments of thedisclosure, the lower limit on the density, d1 of the first polyethylenemay be about 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in othercases about 0.875 g/cm³.

In embodiments of the disclosure the density, d1 of the firstpolyethylene may be from about 0.855 to about 0.965 g/cm³, or from 0.865g/cm³ to about 0.965 g/cm³, or from about 0.870 g/cm³ to about 0.960g/cm³, or from about 0.865 g/cm³ to 0.950 g/cm³, or from about 0.865g/cm³ to about 0.940 g/cm³, or from about 0.865 g/cm³ to about 0.936g/cm³, or from about 0.860 g/cm³ to about 0.932 g/cm³, or from about0.865 g/cm³ to about 0.926 g/cm³, or from about 0.865 g/cm³ to about0.921 g/cm³, or from about 0.865 g/cm³ to about 0.918 g/cm³, or fromabout 0.860 g/cm³ to about 0.916 g/cm³, or from about 0.865 g/cm³ toabout 0.916 g/cm³, or from about 0.870 g/cm³ to about 0.916 g/cm³, orfrom about 0.865 g/cm³ to about 0.912 g/cm³, or from about 0.865 g/cm³to about 0.910 g/cm³, or from about 0.865 g/cm³ to about 0.905 g/cm³, orfrom about 0.865 g/cm³ to about 0.900 g/cm³, or from about 0.855 g/cm³to about 0.900 g/cm³, or from about 0.855 g/cm³ to about 0.905 g/cm³, orfrom about 0.855 g/cm³ to about 0.910 g/cm³.

In embodiments of the disclosure, the upper limit on the CDBI₅₀ of thefirst polyethylene may be about 98 wt %, in other cases about 95 wt %and in still other cases about 90 wt %. In embodiments of thedisclosure, the lower limit on the CDBI₅₀ of the first polyethylene maybe about 70 wt %, in other cases about 75 wt % and in still other casesabout 80 wt %.

In embodiments of the disclosure the melt index of the firstpolyethylene 12¹ may be from about 0.01 dg/min to about 1000 dg/min, orfrom about 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min toabout 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or fromabout 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about10 dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about0.01 dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1dg/min, or less than about 5 dg/min, or less than about 3 dg/min, orless than about 1.0 dg/min, or less than about 0.75 dg/min.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) of from about 50,000 to about 300,000,or from about 50,000 to about 250,000, or from about 60,000 to about250,000, or from about 70,000 to about 250,000 or from about 60,000 toabout 220,000, or from about 70,000 to about 200,000, or from about75,000 to about 200,000, or from about 75,000 to about 175,000; or fromabout 70,000 to about 175,000, or from about 70,000 to about 150,000.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of the second polyethylene.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of the third polyethylene.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of both the second polyethylene and the thirdpolyethylene.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 30 percent of the weightaverage molecular weight, M_(w) of the second polyethylene. For clarity,this means that the absolute difference between the weight averagemolecular weight, M_(w) of the first polyethylene and the weight averagemolecular weight, M_(w) of the second polyethylene divided by the weightaverage molecular weight, M_(w) of the second polyethylene and convertedto a percentage (i.e. [|Mw1−Mw2|/Mw2]×100%) is within 30 percent.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 25 percent of the weightaverage molecular weight, M_(w) of the second polyethylene. In anembodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 20 percent of the weightaverage molecular weight, M_(w) of the second polyethylene. In anembodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 15 percent of the weightaverage molecular weight, M_(w) of the second polyethylene. In anembodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 10 percent of the weightaverage molecular weight, M_(w) of the second polyethylene.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 25 percent of the weightaverage molecular weight, M_(w) of the third polyethylene. For clarity,this means that the absolute difference between the weight averagemolecular weight, M_(w) of the first polyethylene and the weight averagemolecular weight, M_(w) of the third polyethylene divided by the weightaverage molecular weight, M_(w) of the third polyethylene and convertedto a percentage (i.e. [|Mw1−Mw3|/Mw3]×100%) is within 25 percent.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 20 percent of the weightaverage molecular weight, M_(w) of the third polyethylene. In anembodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 15 percent of the weightaverage molecular weight, M_(w) of the third polyethylene. In anembodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 10 percent of the weightaverage molecular weight, M_(w) of the third polyethylene. In anembodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is within 5 percent of the weightaverage molecular weight, M_(w) of the third polyethylene.

In embodiments of the disclosure, the upper limit on the weight percent(wt %) of the first polyethylene in the polyethylene composition (i.e.the weight percent of the first polyethylene based on the total weightof the first, the second and the third polyethylene) may be about 85 wt%, or about 80 wt %, or about 75 wt %, or about 70 wt %, or about 65 wt%, or about 60 wt %, or about 55 wt %. In embodiments of the disclosure,the lower limit on the wt % of the first polyethylene in thepolyethylene composition may be about 10 wt %, or about 15 wt %, orabout 20 wt %, or about 25 wt %, or about 30 wt %, or about 35 wt % orin other cases about 40 wt %.

The Second Polyethylene

In an embodiment of the disclosure, the second polyethylene is made witha single site catalyst, non-limiting examples of which includephosphinimine catalysts, metallocene catalysts, and constrained geometrycatalysts, all of which are well known in the art.

In an embodiment of the disclosure, the second polyethylene is anethylene homopolymer.

In an embodiment of the disclosure, the second polyethylene is anethylene copolymer. Suitable alpha-olefins which may be copolymerizedwith ethylene to make an ethylene copolymer include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene.

In an embodiment of the disclosure, the second polyethylene is ahomogeneously branched ethylene copolymer.

In an embodiment of the disclosure, the second polyethylene is anethylene/1-octene copolymer.

In an embodiment of the disclosure, the second polyethylene is made witha phosphinimine catalyst.

In an embodiment of the disclosure, a phosphinimine catalyst isrepresented by the formula:

(L^(A))_(a)M(Pl)_(b)(Q)_(n)

wherein (L^(A)) represents is cyclopentadienyl-type ligand; M representsa metal atom chosen from of Ti, Zr, and Hf; PI represents aphosphinimine ligand; Q represents an activatable ligand; a is 0 or 1; bis 1 or 2; (a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equals thevalance of the metal M.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current disclosure, so long as thefive-carbon ring which bonds to the metal via eta-5 (or in some caseseta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be chosen from aC₁₋₃₀ hydrocarbyl radical (which hydrocarbyl radical may beunsubstituted or further substituted by for example a halide and/or ahydrocarbyl group; for example a suitable substituted C₁₋₃₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical (each of whichmay be further substituted by for example a halide and/or a hydrocarbylgroup); an amido radical which is unsubstituted or substituted by up totwo C₁₋₈ alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; a silyl radical of theformula —Si(R′)₃ wherein each R′ is independently chosen from hydrogen,a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ aryl or aryloxy radicals; and agermanyl radical of the formula —Ge(R′)₃ wherein R′ is as defineddirectly above.

The phosphinimine ligand, Pl, is defined by the formula:

(R^(p))₃P═N—

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

In an embodiment of the disclosure, the metal, M in the phosphiniminecatalyst is titanium, Ti.

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene is cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)₃PN)TiCl₂.

In an embodiment of the disclosure, the second polyethylene is made witha metallocene catalyst.

In an embodiment of the disclosure, the second polyethylene is made witha bridged metallocene catalyst.

In an embodiment of the disclosure, the second polyethylene is made witha bridged metallocene catalyst having the formula I:

In Formula (I): M is a group 4 metal selected from titanium, zirconiumor hafnium; G is a group 14 element selected from carbon, silicon,germanium, tin or lead; R₁ is a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₂ and R₃are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₄ and R₅are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; and Q isindependently an activatable leaving group ligand.

In the current disclosure, the term “activatable,” means that the ligandQ may be cleaved from the metal center M via a protonolysis reaction orabstracted from the metal center M by suitable acidic or electrophiliccatalyst activator compounds (also known as “co-catalyst” compounds)respectively, examples of which are described below. The activatableligand Q may also be transformed into another ligand which is cleaved orabstracted from the metal center M (e.g. a halide may be converted to analkyl group). Without wishing to be bound by any single theory,protonolysis or abstraction reactions generate an active “cationic”metal center which can polymerize olefins.

In embodiments of the present disclosure, the activatable ligand, Q isindependently chosen from a hydrogen atom; a halogen atom; a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, and a C₆₋₁₀ aryl or aryloxyradical, where each of the hydrocarbyl, alkoxy, aryl, or aryl oxideradicals may be un-substituted or further substituted by one or morehalogen or other group; a C₁₋₈ alkyl; a C₁₋₈ alkoxy; a C₆₋₁₀ aryl oraryloxy; an amido or a phosphido radical, but where Q is not acyclopentadienyl. Two Q ligands may also be joined to one another andform for example, a substituted or unsubstituted diene ligand (e.g.1,3-butadiene); or a delocalized heteroatom containing group such as anacetate or acetamidinate group. In a convenient embodiment of thedisclosure, each Q is independently chosen from a halide atom, a C₁₋₄alkyl radical and a benzyl radical. Particularly suitable activatableligands Q are monoanionic such as a halide (e.g. chloride) or ahydrocarbyl (e.g. methyl, benzyl).

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula: [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂].

In an embodiment of the disclosure the single site catalyst used to makethe second polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂].

In addition to the single site catalyst molecule per se, an activesingle site catalyst system may further include one or more of thefollowing: an alkylaluminoxane co-catalyst and an ionic activator. Thesingle site catalyst system may also optionally include a hinderedphenol.

Although the exact structure of alkylaluminoxane is uncertain, subjectmatter experts generally agree that it is an oligomeric species thatcontain repeating units of the general formula:

(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alkylaluminoxane ismethylaluminoxane (or MAO) wherein each R group is a methyl radical.

In an embodiment of the disclosure, R of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

In an embodiment of the disclosure, the co-catalyst is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneco-catalyst is often used in combination with activatable ligands suchas halogens.

In general, ionic activators are comprised of a cation and a bulkyanion; wherein the latter is substantially non-coordinating.Non-limiting examples of ionic activators are boron ionic activatorsthat are four coordinate with four ligands bonded to the boron atom.Non-limiting examples of boron ionic activators include the followingformulas shown below;

[R⁵]⁺[B(R⁷)₄]⁻

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and

[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ is as defined above.

In both formula a non-limiting example of R⁷ is a pentafluorophenylradical. In general, boron ionic activators may be described as salts oftetra(perfluorophenyl) boron; non-limiting examples include anilinium,carbonium, oxonium, phosphonium and sulfonium salts oftetra(perfluorophenyl)boron with anilinium and trityl (ortriphenylmethylium). Additional non-limiting examples of ionicactivators include: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

Non-limiting example of hindered phenols include butylated phenolicantioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethylphenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

To produce an active single site catalyst system the quantity and moleratios of the three or four components: the single site catalyst, thealkylaluminoxane, the ionic activator, and the optional hindered phenolare optimized.

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene produces no long chain branches, and thesecond polyethylene will contain no measurable amounts of long chainbranches.

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene produces long chain branches, and thesecond polyethylene will contain long chain branches, hereinafter ‘LCB’.LCB is a well-known structural phenomenon in polyethylenes and wellknown to those of ordinary skill in the art. Traditionally, there arethree methods for LCB analysis, namely, nuclear magnetic resonancespectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci.,Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equippedwith a DRI, a viscometer and a low-angle laser light scatteringdetector, for example see W.W. Yau and D. R. Hill, Int. J. Polym. Anal.Charact. 1996; 2:151; and rheology, for example see W. W. Graessley,Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long chainbranch is macromolecular in nature, i.e. long enough to be seen in anNMR spectra, triple detector SEC experiments or rheological experiments.

In embodiments of the disclosure, the upper limit on the molecularweight distribution, M_(w)/M_(n) of the second polyethylene may be about2.8, or about 2.5, or about 2.4, or about 2.3, or about 2.2. Inembodiments of the disclosure, the lower limit on the molecular weightdistribution, M_(w)/M_(n) of the second polyethylene may be about 1.4,or about 1.6, or about 1.7, or about 1.8, or about 1.9.

In embodiments of the disclosure, the second polyethylene has amolecular weight distribution, M_(w)/M_(n) of <2.3, or <2.1, or <2.0 orabout 2.0. In embodiments of the disclosure, the second polyethylene hasa molecular weight distribution, M_(w)/M_(n) of from about 1.7 to about2.2.

In an embodiment of the disclosure, the second polyethylene has from 0to 100 short chain branches per thousand carbon atoms (SCB_(PE-2)). Infurther embodiments, the second polyethylene has from 0 to 30 shortchain branches per thousand carbon atoms (SCB_(PE-2)), or from 0 to 20short chain branches per thousand carbon atoms (SCB_(PE-2)), or from 0to 15 short chain branches per thousand carbon atoms (SCB_(PE-2)), orfrom 0 to 10 short chain branches per thousand carbon atoms(SCB_(PE-2)), or from 0 to 5 short chain branches per thousand carbonatoms (SCB_(PE-2)), or fewer than 5 short chain branches per thousandcarbon atoms (SCB_(PE-2)), or fewer than 3 short chain branches perthousand carbon atoms (SCB_(PE-2)), or fewer than 1 short chain branchesper thousand carbon atoms (SCBPE2) , or about zero short chain branchesper thousand carbon atoms (SCB_(PE-2)).

The short chain branching (i.e. the short chain branching per thousandcarbons, SCB_(PE-2)) is the branching due to the presence of analpha-olefin comonomer in the polyethylene and will for example have twocarbon atoms for a 1-butene comonomer, or four carbon atoms for a1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.

In embodiments of the disclosure, the upper limit on the density, d2 ofthe second polyethylene may be about 0.985 g/cm³; in some cases about0.975 g/cm³ and; in other cases about 0.965 g/cm³. In embodiments of thedisclosure, the lower limit on the density, d2 of the secondpolyethylene may be about 0.916 g/cm³, or about 0.921 g/cm³, in somecases about 0.930 g/cm³, and; in other cases about 0.940 g/cm³.

In embodiments of the disclosure the density, d2 of the secondpolyethylene may be from about 0.916 g/cm³ to about 0.980 g/cm³, or fromabout 0.921 g/cm³ to about 0.980 g/cm³, or from about 0.921 g/cm³ toabout 0.975 g/cm³, or from about 0.926 g/cm³ to about 0.975 g/cm³, orfrom about 0.930 g/cm³ to about 0.980 g/cm³, or from about 0.930 g/cm³toabout 0.975 g/cm³, or from about 0.936 g/cm³ to about 0.975 g/cm³, orfrom about 0.940 g/cm³ to about 0.975 g/cm³, or from about 0.940 g/cm³to about 0.980 g/cm³, or from about 0.943 g/cm³ to about 0.975 g/cm³.

In embodiments of the disclosure the melt index of the secondpolyethylene 12² may be from about 0.01 dg/min to about 1000 dg/min, orfrom about 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min toabout 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or fromabout 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about10 dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about0.01 dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1dg/min, or less than about 5 dg/min, or less than about 3 dg/min, orless than about 1.0 dg/min.

In an embodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) of from about 50,000 to about 275,000,or from about 50,000 to about 250,000, or from about 50,000 to about200,000, or from about 60,000 to about 250,000, or from about 70,000 toabout 250,000 or from about 60,000 to about 220,000, or from about70,000 to about 200,000, or from about 75,000 to about 200,000, or fromabout 75,000 to about 175,000; or from about 70,000 to about 175,000, orfrom about 70,000 to about 150,000, or from about 60,000 to about140,000, or from about 50,000 to about 150,000, or from about 60,000 toabout 150,000.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene is less than the weight average molecularweight of the first polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene is less than the weight average molecularweight of the third polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene is less than the weight average molecularweight of the first polyethylene and the third polyethylene.

In an embodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 30 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. For clarity,this means that the absolute difference between the weight averagemolecular weight, M_(w) of the second polyethylene and the weightaverage molecular weight, M_(w) of the first polyethylene divided by theweight average molecular weight, M_(w) of the first polyethylene andconverted to a percentage (i.e. [|Mw2−Mw1|/Mw1]×100%) is within 30percent.

In an embodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 25 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. In anembodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 20 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. In anembodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 15 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. In anembodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 10 percent of the weightaverage molecular weight, M_(w) of the first polyethylene.

In an embodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 25 percent of the weightaverage molecular weight, M_(w) of the third polyethylene. For clarity,this means that the absolute difference between the weight averagemolecular weight, M_(w) of the second polyethylene and the weightaverage molecular weight, M_(w) of the third polyethylene divided by theweight average molecular weight, M_(w) of the third polyethylene andconverted to a percentage (i.e. [|Mw2−Mw3|/Mw3]×100%) is within 25percent.

In an embodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 20 percent of the weightaverage molecular weight, M_(w) of the third polyethylene. In anembodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 15 percent of the weightaverage molecular weight, M_(w) of the third polyethylene. In anembodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) which is within 10 percent of the weightaverage molecular weight, M_(w) of the third polyethylene.

In embodiments of the disclosure, the upper limit on the weight percent(wt %) of the second polyethylene in the polyethylene composition (i.e.the weight percent of the second polyethylene based on the total weightof the first, the second and the third polyethylene) may be about 75 wt%, or about 70 wt %, or about 65 wt %, or about 60 wt %, or about 55 wt%, or about 50 wt %, or about 45 wt %, or about 40 wt %. In embodimentsof the disclosure, the lower limit on the wt % of the secondpolyethylene in the polyethylene composition may be about 5 wt %, orabout 10 wt %, or about 15 wt %, or about 20 wt %.

The Third Polyethylene

In an embodiment of the disclosure, the third polyethylene is made witha single site catalyst, non-limiting examples of which includephosphinimine catalysts, metallocene catalysts, and constrained geometrycatalysts, all of which are well known in the art.

In an embodiment of the disclosure, the third polyethylene is anethylene copolymer. Suitable alpha-olefins which may be copolymerizedwith ethylene to make an ethylene copolymer include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene.

In an embodiment of the disclosure, the third polyethylene is ahomogeneously branched ethylene copolymer.

In an embodiment of the disclosure, the third polyethylene is anethylene/1-octene copolymer.

In an embodiment of the disclosure, the third polyethylene is anethylene homopolymer.

In an embodiment of the disclosure, the third polyethylene is made witha phosphinimine catalyst.

In an embodiment of the disclosure, a phosphinimine catalyst isrepresented by the formula:

(L^(A))_(a)M(Pl)_(b)(Q)_(n)

wherein (L^(A)) represents is cyclopentadienyl-type ligand; M representsa metal atom chosen from Ti, Zr, and Hf; Pl represents a phosphinimineligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2;(a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of themetal M.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current disclosure, so long as thefive-carbon ring which bonds to the metal via eta-5 (or in some caseseta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be chosen from aC₁₋₃₀ hydrocarbyl radical (which hydrocarbyl radical may beunsubstituted or further substituted by for example a halide and/or ahydrocarbyl group; for example a suitable substituted C₁₋₃₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical (each of whichmay be further substituted by for example a halide and/or a hydrocarbylgroup); an amido radical which is unsubstituted or substituted by up totwo C₁₋₈ alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; a silyl radical of theformula —Si(R′)₃ wherein each R′ is independently chosen from hydrogen,a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ aryl or aryloxy radicals; and agermanyl radical of the formula —Ge(R′)₃ wherein R′ is as defineddirectly above.

The phosphinimine ligand, PI, is defined by the formula:

(R^(p))₃P═N—

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

In an embodiment of the disclosure, the metal, M in the phosphiniminecatalyst is titanium, Ti.

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene is cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)₃PN)TiCl₂.

In an embodiment of the disclosure, the third polyethylene is made witha metallocene catalyst.

In an embodiment of the disclosure, the third polyethylene is made witha bridged metallocene catalyst.

In an embodiment of the disclosure, the third polyethylene is made witha bridged metallocene catalyst having the formula I:

In Formula (I): M is a group 4 metal selected from titanium, zirconiumor hafnium; G is a group 14 element selected from carbon, silicon,germanium, tin or lead; R₁ is a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R2 and R3are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₄ and R₅are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; and Q isindependently an activatable leaving group ligand.

In the current disclosure, the term “activatable,” means that the ligandQ may be cleaved from the metal center M via a protonolysis reaction orabstracted from the metal center M by suitable acidic or electrophiliccatalyst activator compounds (also known as “co-catalyst” compounds)respectively, examples of which are described below. The activatableligand Q may also be transformed into another ligand which is cleaved orabstracted from the metal center M (e.g. a halide may be converted to analkyl group). Without wishing to be bound by any single theory,protonolysis or abstraction reactions generate an active “cationic”metal center which can polymerize olefins.

In embodiments of the present disclosure, the activatable ligand, Q isindependently chosen from a hydrogen atom; a halogen atom; a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, and a C₆₋₁₀ aryl or aryloxyradical, where each of the hydrocarbyl, alkoxy, aryl, or aryl oxideradicals may be un-substituted or further substituted by one or morehalogen or other group; a C₁₋₈ alkyl; a C₁₋₈ alkoxy; a C₆₋₁₀ aryl oraryloxy; an amido or a phosphido radical, but where Q is not acyclopentadienyl. Two Q ligands may also be joined to one another andform for example, a substituted or unsubstituted diene ligand (e.g.1,3-butadiene); or a delocalized heteroatom containing group such as anacetate or acetamidinate group. In a convenient embodiment of thedisclosure, each Q is independently chosen from a halide atom, a C₁₋₄alkyl radical and a benzyl radical. Particularly suitable activatableligands Q are monoanionic such as a halide (e.g. chloride) or ahydrocarbyl (e.g. methyl, benzyl).

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula: [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂].

In an embodiment of the disclosure the single site catalyst used to makethe third polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂].

In addition to the single site catalyst molecule per se, an activesingle site catalyst system may further include one or more of thefollowing: an alkylaluminoxane co-catalyst and an ionic activator. Thesingle site catalyst system may also optionally include a hinderedphenol.

Although the exact structure of alkylaluminoxane is uncertain, subjectmatter experts generally agree that it is an oligomeric species thatcontain repeating units of the general formula:

(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alkylaluminoxane ismethylaluminoxane (or MAO) wherein each R group is a methyl radical.

In an embodiment of the disclosure, R of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

In an embodiment of the disclosure, the co-catalyst is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneco-catalyst is often used in combination with activatable ligands suchas halogens.

In general, ionic activators are comprised of a cation and a bulkyanion; wherein the latter is substantially non-coordinating.Non-limiting examples of ionic activators are boron ionic activatorsthat are four coordinate with four ligands bonded to the boron atom.Non-limiting examples of boron ionic activators include the followingformulas shown below;

[R⁵]⁺[B(R⁷)₄]⁻

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula -Si(R⁹)3, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and

[R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ is as defined above.

In both formula a non-limiting example of R⁷ is a pentafluorophenylradical. In general, boron ionic activators may be described as salts oftetra(perfluorophenyl) boron; non-limiting examples include anilinium,carbonium, oxonium, phosphonium and sulfonium salts oftetra(perfluorophenyl)boron with anilinium and trityl (ortriphenylmethylium). Additional non-limiting examples of ionicactivators include: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

Non-limiting example of hindered phenols include butylated phenolicantioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethylphenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

To produce an active single site catalyst system the quantity and moleratios of the three or four components: the single site catalyst, thealkylaluminoxane, the ionic activator, and the optional hindered phenolare optimized.

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene produces no long chain branches, and thethird polyethylene will contain no measurable amounts of long chainbranches.

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene produces long chain branches, and the thirdpolyethylene will contain long chain branches, hereinafter “LCB”. LCB isa well-known structural phenomenon in polyethylenes and well known tothose of ordinary skill in the art. Traditionally, there are threemethods for LCB analysis, namely, nuclear magnetic resonancespectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci.,Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equippedwith a DRI, a viscometer and a low-angle laser light scatteringdetector, for example see W. W. Yau and D. R. Hill, Int. J. Polym. Anal.Charact. 1996; 2:151; and rheology, for example see W.W. Graessley, Acc.Chem. Res. 1977, 10, 332-339. In this disclosure, a long chain branch ismacromolecular in nature, i.e. long enough to be seen in an NMR spectra,triple detector SEC experiments or rheological experiments.

In embodiments of the disclosure, the upper limit on the molecularweight distribution, M_(w)/M_(n) of the third polyethylene may be about2.8, or about 2.5, or about 2.4, or about 2.3, or about 2.2. Inembodiments of the disclosure, the lower limit on the molecular weightdistribution, M_(w)/M_(n) of the third polyethylene may be about 1.4, orabout 1.6, or about 1.7, or about 1.8, or about 1.9.

In embodiments of the disclosure, the third polyethylene has a molecularweight distribution, M_(w)/M_(n) of <2.3, or <2.1, or <2.0 or about 2.0.In embodiments of the disclosure, the third polyethylene has a molecularweight distribution, M_(w)/M_(n) of from about 1.7 to about 2.2.

In an embodiment of the disclosure, the third polyethylene has from 0 to100 short chain branches per thousand carbon atoms (SCB_(PE-3)). Infurther embodiments, the third polyethylene has from 0 to 30 short chainbranches per thousand carbon atoms (SCB_(PE-3)), or from 0 to 20 shortchain branches per thousand carbon atoms (SCB_(PE-3)), or from 0 to 15short chain branches per thousand carbon atoms (SCB_(PE-3)), or from 0to 10 short chain branches per thousand carbon atoms (SCB_(PE-3)), orfrom 0 to 5 short chain branches per thousand carbon atoms (SCB_(PE-3)),or fewer than 5 short chain branches per thousand carbon atoms(SCB_(PE-3)), or fewer than 3 short chain branches per thousand carbonatoms (SCB_(PE-3)), or fewer than 1 short chain branches per thousandcarbon atoms (SCB_(PE-3)) , or about 0.1 to about 1.0 short chainbranches per thousand carbon atoms (SCB_(PE-3)), or about 0.1 to about 5short chain branches per thousand carbon atoms (SCB_(PE-3)).

The short chain branching (i.e. the short chain branching per thousandcarbons, SCB_(PE-3)) is the branching due to the presence of analpha-olefin comonomer in the polyethylene and will for example have twocarbon atoms for a 1-butene comonomer, or four carbon atoms for a1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the third polyethylene (SCB_(PE-3)) isgreater than the number of short chain branches per thousand carbonatoms in the second polyethylene (SCB_(PE-2)).

In embodiments of the disclosure, the upper limit on the density, d3 ofthe third polyethylene may be about 0.985 g/cm³; in some cases about0.975 g/cm³ and; in other cases about 0.965 g/cm³. In embodiments of thedisclosure, the lower limit on the density, d3 of the third polyethylenemay be about 0.916 g/cm³, or about 0.921 g/cm³, in some cases about0.930 g/cm³, and; in other cases about 0.940 g/cm³.

In embodiments of the disclosure the density, d3 of the thirdpolyethylene may be from about 0.916 g/cm³ to about 0.980 g/cm³, or fromabout 0.921 g/cm³ to about 0.980 g/cm³, or from about 0.921 g/cm³ toabout 0.975 g/cm³, or from about 0.926 g/cm³ to about 0.975 g/cm³, orfrom about 0.930 g/cm³ to about 0.980 g/cm³, or from about 0.930 g/cm³toabout 0.975 g/cm³, or from about 0.936 g/cm³ to about 0.975 g/cm³, orfrom about 0.940 g/cm³ to about 0.975 g/cm³, or from about 0.940 g/cm³toabout 0.980 g/cm³, or from about 0.943 g/cm³ to about 0.975 g/cm³.

In embodiments of the disclosure the melt index of the thirdpolyethylene I2³ may be from about 0.01 dg/min to about 1000 dg/min, orfrom about 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min toabout 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or fromabout 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about10 dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about0.01 dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1dg/min, or less than about 5 dg/min, or less than about 3 dg/min, orless than about 1.0 dg/min.

In embodiments of the disclosure, the upper limit on the CDB 150 of thethird polyethylene may be about 98 wt %, in other cases about 95 wt %and in still other cases about 90 wt %. In embodiments of thedisclosure, the lower limit on the CDBI₅₀ of the third polyethylene maybe about 70 wt %, in other cases about 75 wt % and in still other casesabout 80 wt %.

In an embodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) of from about 50,000 to about 275,000,or from about 50,000 to about 250,000, or from about 60,000 to about250,000, or from about 70,000 to about 250,000 or from about 60,000 toabout 220,000, or from about 70,000 to about 200,000, or from about75,000 to about 200,000, or from about 75,000 to about 175,000; or fromabout 70,000 to about 175,000, or from about 70,000 to about 150,000, orfrom about 60,000 to about 140,000.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene is less than the weight average molecularweight of the first polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene is greater than the weight average molecularweight of the second polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene is less than the weight average molecularweight of the first polyethylene and greater than the weight averagemolecular weight of the second polyethylene.

In an embodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 25 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. For clarity,this means that the absolute difference between the weight averagemolecular weight, M_(w) of the third polyethylene and the weight averagemolecular weight, M_(w) of the first polyethylene divided by the weightaverage molecular weight, M_(w) of the first polyethylene and convertedto a percentage (i.e. [|Mw3−Mw1|/Mw1]×100%) is within 25 percent.

In an embodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 20 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. In anembodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 15 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. In anembodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 10 percent of the weightaverage molecular weight, M_(w) of the first polyethylene. In anembodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 5 percent of the weightaverage molecular weight, M_(w) of the first polyethylene.

In an embodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 25 percent of the weightaverage molecular weight, M_(w) of the second polyethylene. For clarity,this means that the absolute difference between the weight averagemolecular weight, M_(w) of the third polyethylene and the weight averagemolecular weight, M_(w) of the second polyethylene divided by the weightaverage molecular weight, M_(w) of the second polyethylene and convertedto a percentage (i.e. [|Mw3−Mw2|/Mw2]×100%) is within 30 percent.

In an embodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 20 percent of the weightaverage molecular weight, M_(w) of the second polyethylene. In anembodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 15 percent of the weightaverage molecular weight, M_(w) of the second polyethylene. In anembodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) which is within 10 percent of the weightaverage molecular weight, M_(w) of the second polyethylene.

In embodiments of the disclosure, the upper limit on the weight percent(wt %) of the third polyethylene in the polyethylene composition (i.e.the weight percent of the third polyethylene based on the total weightof the first, the second and the third polyethylene) may be about 75 wt%, or about 70 wt %, or about 65 wt %, or about 60 wt %, or about 55 wt%, or about 50 wt %, or about 45 wt %, or about 40 wt %, or about 35 wt%, or about 30 wt %. In embodiments of the disclosure, the lower limiton the wt % of the third polyethylene in the polyethylene compositionmay be about 5 wt %, or about 10 wt %, or about 15 wt %.

The Polyethylene Composition

The polyethylene compositions disclosed herein can be made using anywell-known techniques in the art, including but not limited to meltblending, solution blending, or in-reactor blending to bring together afirst polyethylene, a second polyethylene and a third polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending three differentpolyethylene components: i) a first polyethylene, ii) a secondpolyethylene, and iii) a third polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending two different polyethylenecomponents: i) a first polyethylene component including a firstpolyethylene and a second polyethylene, and ii) second polyethylenecomponent including a third polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending two different polyethylenecomponents: i) a first polyethylene component including a firstpolyethylene and ii) a second polyethylene component including a secondpolyethylene and a third polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending two different polyethylenecomponents: i) a first polyethylene component including a firstpolyethylene and a third polyethylene, and ii) a second polyethylenecomponent including a second polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made using the same single site catalyst in three different reactors,where each reactor is operated under different polymerization conditionsto give a first polyethylene, a second polyethylene and a thirdpolyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made using the same or different single site catalysts in threedifferent reactors, where each reactor is operated under differentpolymerization conditions to give a first polyethylene, a secondpolyethylene and a third polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made using a different single site catalyst in each of threedifferent reactors, where each reactor is operated under similar ordifferent polymerization conditions to give a first polyethylene, asecond polyethylene and a third polyethylene.

It is also contemplated by the present disclosure, that the polymercompositions including a first, second and third polyethylene could bemade in a single polymerization reactor, using three different singlesite polymerization catalysts, where each catalyst has a differentresponse to one or more of hydrogen concentration, ethyleneconcentration, comonomer concentration, and temperature under a givenset of polymerization conditions, so that the first polyethylene isproduced by the first single site catalyst, the second polyethylene isproduced by the second single site catalyst, and the third polyethyleneis produced by the third single site catalyst.

It is also contemplated by the present disclosure, that the polymercompositions including a first, second and third polyethylene could bemade in one or more polymerization reactors, using one or more singlesite polymerization catalysts, where each catalyst has a similar ordifferent response to one or more of hydrogen concentration, ethyleneconcentration, comonomer concentration, and temperature under a givenset of polymerization conditions, and where one or more of hydrogenconcentration, ethylene concentration, comonomer concentration, andtemperature are cycled through a range so that a first, second and athird polyethylene is produced by the one or more single site catalystspresent in the one or more polymerization reactors.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with a single site catalyst, andforming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with a single site catalyst, andforming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst, where atleast two of the first, second and third reactors are configured inseries with one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, and forming athird polyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, and forming athird polyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst, where at least two of the first, second and third solutionphase polymerization reactors are configured in series with one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, and forming athird polyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst, where the first and second solution phase polymerizationreactors are configured in series with one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with a single site catalyst, andforming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst, where eachof the first, second and third reactors are configured in parallel toone another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, and forming athird polyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst, where each of the first, second and third solution phasepolymerization reactors are configured in parallel to one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with a single site catalyst, andforming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst, where thefirst and second reactors are configured in series to one another, andthe third reactor is configured in parallel to the first and secondreactors.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasereactor by polymerizing ethylene and an alpha olefin with a single sitecatalyst; forming a second polyethylene in a second solution phasereactor by polymerizing ethylene and optionally an alpha olefin with asingle site catalyst, and forming a third polyethylene in a thirdsolution phase reactor by polymerizing ethylene and optionally an alphaolefin with a single site catalyst, where the first and second solutionphase reactors are configured in series to one another, and the thirdsolution phase reactor is configured in parallel to the first and secondreactors.

In an embodiment, the solution phase polymerization reactor used as afirst solution phase reactor, a second solution phase reactor, or athird solution phase reactor is a continuously stirred tank reactor.

In an embodiment, the solution phase polymerization reactor used as afirst solution phase reactor, a second solution phase reactor, or athird solution phase reactor is a tubular reactor.

In a solution phase polymerization reactor, a variety of solvents may beused as the process solvent; non-limiting examples include linear,branched or cyclic C₅ to C₁₂ alkanes. Non-limiting examples of α-olefinsinclude 1-propene, 1-butene, 1-pentene, 1-hexene and 1-octene. Suitablecatalyst component solvents include aliphatic and aromatic hydrocarbons.Non-limiting examples of aliphatic catalyst component solvents includelinear, branched or cyclic C₅₋₁₂ aliphatic hydrocarbons, e.g. pentane,methyl pentane, hexane, heptane, octane, cyclohexane, cyclopentane,methylcyclohexane, hydrogenated naphtha or combinations thereof.Non-limiting examples of aromatic catalyst component solvents includebenzene, toluene (methylbenzene), ethylbenzene, o-xylene(1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene(1,4-dimethylbenzene), mixtures of xylene isomers, hemellitene(1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene),mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzeneisomers, prehenitene (1,2,3,4-tetramethylbenzene), durene(1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene isomers,pentamethylbenzene, hexamethylbenzene and combinations thereof.

In embodiments of the disclosure, the polyethylene composition has adensity which may be from about 0.880 g/cm³ to about 0.965 g/cm³, orfrom about 0.885 g/cm³ to about 0.960 g/cm³, or from about 0.890 g/cm³to 0.950 g/cm³, or from about 0.895 g/cm³ to about 0.940 g/cm³, or fromabout 0.900 g/cm³ to about 0.936 g/cm³, or from about 0.905 g/cm³ toabout 0.934 g/cm³, or from about 0.910 g/cm³ to about 0.932 g/cm³, orfrom about 0.910 g/cm³ to about 0.930 g/cm³, or from about 0.910 g/cm³to about 0.926 g/cm³, or from about 0.890 g/cm³ to about 0.924 g/cm³, orfrom about 0.890 g/cm³ to about 0.922 g/cm³, or from about 0.890 g/cm³to about 0.920 g/cm³, or from about 0.890 g/cm³ to about 0.918 g/cm³, orfrom about 0.880 g/cm³ to about 0.922 g/cm³, or from about 0.880 g/cm³to about 0.926 g/cm³, or from about 0.880 g/cm³ to about 0.932 g/cm³, or≤0.948 g/cm³, or <0.948 g/cm³, or ≤0.945 g/cm³, or <0.945 g/cm³, or≤0.940 g/cm³, or <0.940 g/cm³, or ≤0.939 g/cm³, or <0.939 g/cm³, or≤0.935 g/cm³, or <0.935 g/cm³, or ≤0.932 g/cm³, or <0.932 g/cm³.

In embodiments of the disclosure the melt index I₂ of the polyethylenecomposition may be from about 0.01 dg/min to about 1000 dg/min, or fromabout 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min toabout 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or fromabout 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about10 dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about0.01 dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1dg/min, or from about 0.1 dg/min to about 10 dg/min, or from about 0.1dg/min to about 5 dg/min, or from about 0.1 dg/min to about 3 dg/min, orfrom about 0.1 dg/min to about 2 dg/min, or from about 0.1 dg/min toabout 1.5 dg/min, or from about 0.1 dg/min to about 1 dg/min, or lessthan about 5 dg/min, or less than about 3 dg/min, or less than about 1.0dg/min.

In embodiments of the disclosure the high load melt index I₂₁ of thepolyethylene composition may be from about 1 dg/min to about 10,000dg/min, or from about 3 dg/min to about 1000 dg/min, or from about 5dg/min to about 100 dg/min, or from about 5 dg/min to about 75 dg/min,or from about 5 dg/min to about 50 dg/min, or from about 3 dg/min toabout 100 dg/min, or from about 3 dg/min to about 75 dg/min, or fromabout 3 dg/min to about 50 dg/min, or from about 3 dg/min to about 45dg/min, or from about 5 dg/min to about 40 dg/min, or from about 5dg/min to about 30 dg/min, or from about 5 dg/min to about 25 dg/min, orfrom about 3 dg/min to about 20 dg/min.

In embodiments of the disclosure the melt flow ratio I₂₁/I₂ of thepolyethylene composition may be from about 15 to about 1000, or fromabout 15 to about 100, or from about 15 to about 75, or from about 15 toabout 50, or from 15 to about 40, or from about 17 to about 40, or fromabout 17 to about 30, or from about 17 to about 28, or from about 17 toabout 25, or from about 18 to about 22.

In an embodiments of the disclosure, the polyethylene composition has aweight average molecular weight, M_(w) of from about 50,000 to about300,000, or from about 50,000 to about 250,000, or from about 60,000 toabout 250,000, or from about 70,000 to about 225,000, or from about70,000 to about 200,000, or from about 75,000 to about 175,000, or fromabout 75,000 to about 150,000, or from about 75,000 to about 125,000.

In embodiments of the disclosure, the polyethylene composition has amolecular weight distribution, M_(w)/M_(n) of ≤3.5, or <3.5, or ≤3.0, or<3.0, or ≤2.5, or <2.5, or ≤2.3, or ≤2.1, or ≤2.0. In embodiments of thedisclosure, the polyethylene composition has a molecular weightdistribution, M_(w)/M_(n) of from 1.5 to 3.5, or from 1.5 to 3.0, orfrom 1.5 to 2.5, or from 1.5 to 2.3, or from 1.5 to 2.1, or from 1.6 to2.5, or from 1.6 to 2.3, or from 1.6 to 2.1.

In embodiments of the disclosure, the polyethylene composition has aZ-average molecular weight distribution, Mz/Mw of ≤3.0, or <3.0, or≤2.5, or <2.5, or ≤2.3, or <2.3, or ≤2.0, or <2.0, or ≤1.75, or <1.75,or ≤1.60, or <1.60. In embodiments of the disclosure, the polyethylenecomposition has a Z-average molecular weight distribution, Mz/Mw of from1.3 to 3.0, or from 1.3 to 2.5, or from 1.3 to 2.25, or from 1.5 to2.25, or from 1.5 to 2.0.

In an embodiment of the disclosure, the polyethylene composition has aunimodal profile in a gel permeation chromatograph generated accordingto the method of ASTM D6474-99. The term “unimodal” is herein defined tomean there will be only one significant peak or maximum evident in theGPC-curve. A unimodal profile includes a broad unimodal profile. Incontrast, the use of the term “bimodal” is meant to convey that inaddition to a first peak, there will be a secondary peak or shoulderwhich represents a higher or lower molecular weight component (i.e. themolecular weight distribution, can be said to have two maxima in amolecular weight distribution curve). Alternatively, the term “bimodal”connotes the presence of two maxima in a molecular weight distributioncurve generated according to the method of ASTM D6474-99. The term“multi-modal” denotes the presence of two or more, typically more thantwo, maxima in a molecular weight distribution curve generated accordingto the method of ASTM D6474-99.

In an embodiment of the disclosure the polyethylene composition may havea multimodal profile in a differential scanning calorimetry (DSC) graph.In the context of DSC analysis, the term “multimodal” connotes a DSCprofile in which two or more distinct melting peaks are observable.

In an embodiment of the disclosure the polyethylene composition may havea trimodal profile in a differential scanning calorimetry (DSC) graph.In the context of DSC analysis, the term “trimodal” connotes a DSCprofile in which three distinct melting peaks are observable.

In an embodiment of the disclosure, the polyethylene composition has amelting peak temperature in a differential scanning calorimetry (DSC)analysis at above 120° C. For clarity sake, by the phrase “has a meltingpeak temperature in an DSC analysis” it is meant that in a DSC analysis,although there may be one or more melting peaks evident, at least onesuch peak occurs at above the indicated temperature. In an embodiment ofthe disclosure, the polyethylene composition has a melting peaktemperature in a differential scanning calorimetry (DSC) analysis atabove 123° C. In an embodiment of the disclosure, the polyethylenecomposition has a melting peak temperature in a differential scanningcalorimetry (DSC) analysis at above 125° C.

In an embodiment of the disclosure, the polyethylene composition has amelting peak temperature in a differential scanning calorimetry (DSC)analysis at below 100° C. For clarity sake, by the phrase “has a meltingpeak temperature in an DSC analysis” it is meant that in a DSC analysis,although there may be one or more melting peaks evident, at least onesuch peak occurs at below the indicated temperature. In an embodiment ofthe disclosure, the polyethylene composition has a melting peaktemperature in a differential scanning calorimetry (DSC) analysis atbelow 95° C. In an embodiment of the disclosure, the polyethylenecomposition has a melting peak temperature in a differential scanningcalorimetry (DSC) analysis at below 90° C. In an embodiment of thedisclosure, the polyethylene composition has a melting peak temperaturein a differential scanning calorimetry (DSC) analysis at below 85° C. Inan embodiment of the disclosure, the polyethylene composition has amelting peak temperature in a differential scanning calorimetry (DSC)analysis at below 80° C.

In an embodiment of the disclosure, the polyethylene composition willhave will have a reverse or partially reverse comonomer distributionprofile as measured using GPC-FTIR. If the comonomer incorporationdecreases with molecular weight, as measured using GPC-FTIR, thedistribution is described as “normal”. If the comonomer incorporation isapproximately constant with molecular weight, as measured usingGPC-FTIR, the comonomer distribution is described as “flat” or“uniform”. The terms “reverse comonomer distribution” and “partiallyreverse comonomer distribution” mean that in the GPC-FTIR data obtainedfor a copolymer, there is one or more higher molecular weight componentshaving a higher comonomer incorporation than in one or more lowermolecular weight components. The term “reverse(d) comonomerdistribution” is used herein to mean, that across the molecular weightrange of an ethylene copolymer, comonomer contents for the variouspolymer fractions are not substantially uniform and the higher molecularweight fractions thereof have proportionally higher comonomer contents(i.e. if the comonomer incorporation rises with molecular weight, thedistribution is described as “reverse” or “reversed”). Where thecomonomer incorporation rises with increasing molecular weight and thendeclines, the comonomer distribution is still considered “reverse”, butmay also be described as “partially reverse”. A partially reversecomonomer distribution will exhibit a peak or maximum.

In an embodiment of the disclosure the polyethylene composition has areversed comonomer distribution profile as measured using GPC-FTIR.

In an embodiment of the disclosure the polyethylene composition has apartially reversed comonomer distribtuion profile as measured usingGPC-FTIR.

In an embodiment of the disclosure, the polyethylene composition has acomposition distribution breadth index, CDBI₅₀ obtained from acrystallization elution fractionation (CEF) analysis, of less than 50weight percent (wt %). In an embodiment of the disclosure, thepolyethylene composition has a composition distribution breadth index,CDBI₅₀ obtained from a crystallization elution fractionation (CEF)analysis, of less than 45 weight percent (wt %). In an embodiment of thedisclosure, the polyethylene composition has a composition distributionbreadth index, CDBI₅₀ obtained from a crystallization elutionfractionation (CEF) analysis, of less than 40 weight percent (wt %). Inan embodiment of the disclosure, the polyethylene composition has acomposition distribution breadth index, CDBI₅₀ obtained from acrystallization elution fractionation (CEF) analysis, of less than 35weight percent (wt %). In an embodiment of the disclosure, thepolyethylene composition has a composition distribution breadth index,CDBI₅₀obtained from a crystallization elution fractionation (CEF)analysis, of less than 30 weight percent (wt %). In an embodiment of thedisclosure, the polyethylene composition has a composition distributionbreadth index, CDBI₅₀ obtained from a crystallization elutionfractionation (CEF) analysis, of less than 25 weight percent (wt %).

In an embodiment of the disclosure, the polyethylene composition has acomposition distribution breadth index, CDBI₅₀ obtained from acrystallization elution fractionation (CEF) analysis, of from 15 to 30weight percent (wt %).

In an embodiment of the disclosure, the polyethylene composition has astress exponent, defined as Log₁₀[I₆/I₂]/Log₁₀[6.48/2.16], which is≤1.40. In further embodiments of the disclosure the polyethylenecomposition has a stress exponent, Log₁₀[I₆/I₂]/Log₁₀[6.48/2.16] of lessthan 1.35, or less than 1.30, or less than 1.25.

In an embodiment of the disclosure, the polyethylene composition has ahexane extractable value of 5.0 weight percent, or less than 4.0 wt %,or less than 3.0 wt %, or less than 2.0 wt %, or less than 1.0 wt %.

The polyethylene composition disclosed herein may be converted intoflexible manufactured articles such as monolayer or multilayer films.Such films are well known to those experienced in the art; non-limitingexamples of processes to prepare such films include blown film and castfilm processes.

In the blown film extrusion process an extruder heats, melts, mixes andconveys a thermoplastic, or a thermoplastic blend. Once molten, thethermoplastic is forced through an annular die to produce athermoplastic tube. In the case of co-extrusion, multiple extruders areemployed to produce a multilayer thermoplastic tube. The temperature ofthe extrusion process is primarily determined by the thermoplastic orthermoplastic blend being processed, for example the melting temperatureor glass transition temperature of the thermoplastic and the desiredviscosity of the melt. In the case of polyolefins, typical extrusiontemperatures are from 330° F. to 550° F. (166° C. to 288° C.). Upon exitfrom the annular die, the thermoplastic tube is inflated with air,cooled, solidified and pulled through a pair of nip rollers. Due to airinflation, the tube increases in diameter forming a bubble of desiredsize. Due to the pulling action of the nip rollers the bubble isstretched in the machine direction. Thus, the bubble is stretched in twodirections: the transverse direction (TD) where the inflating airincreases the diameter of the bubble; and the machine direction (MD)where the nip rollers stretch the bubble. As a result, the physicalproperties of blown films are typically anisotropic, i.e. the physicalproperties differ in the MD and TD directions; for example, film tearstrength and tensile properties typically differ in the MD and TD. Insome documents, the terms “cross direction” or “CD” is used; these termsare equivalent to the terms “transverse direction” or “TD” used in thisdisclosure. In the blown film process, air is also blown on the externalbubble circumference to cool the thermoplastic as it exits the annulardie. The final width of the film is determined by controlling theinflating air or the internal bubble pressure; in other words,increasing or decreasing bubble diameter. Film thickness is controlledprimarily by increasing or decreasing the speed of the nip rollers tocontrol the draw-down rate. After exiting the nip rollers, the bubble ortube is collapsed and may be slit in the machine direction thus creatingsheeting. Each sheet may be wound into a roll of film. Each roll may befurther slit to create film of the desired width. Each roll of film isfurther processed into a variety of consumer products as describedbelow.

The cast film process is similar in that a single or multipleextruder(s) may be used; however the various thermoplastic materials aremetered into a flat die and extruded into a monolayer or multilayersheet, rather than a tube. In the cast film process the extruded sheetis solidified on a chill roll.

Depending on the end-use application, the disclosed polyethylenecomposition may be converted into films that span a wide range ofthicknesses. Non-limiting examples include, food packaging films wherethicknesses may range from about 0.5 mil (13 μm) to about 4 mil (102μm), and; in heavy duty sack applications film thickness may range fromabout 2 mil (51μm) to about 10 mil (254 μm).

The polyethylene composition disclosed herein may be used in monolayerfilms; where the monolayer may contain more than one polyethylenecomposition and/or additional thermoplastics; non-limiting examples ofthermoplastics include polyethylene polymers and propylene polymers. Thelower limit on the weight percent of the polyethylene composition in amonolayer film may be about 3 wt %, in other cases about 10 wt % and instill other cases about 30 wt %. The upper limit on the weight percentof the polyethylene composition in the monolayer film may be 100 wt %,in other cases about 90 wt % and in still other cases about 70 wt %.

The polyethylene composition disclosed herein may also be used in one ormore layers of a multilayer film; non-limiting examples of multilayerfilms include three, five, seven, nine, eleven or more layers. Thethickness of a specific layer (containing the polyethylene composition)within a multilayer film may be about 5%, in other cases about 15% andin still other cases about 30% of the total multilayer film thickness.In other embodiments, the thickness of a specific layer (containing thepolyethylene composition) within a multilayer film may be about 95%, inother cases about 80% and in still other cases about 65% of the totalmultilayer film thickness. Each individual layer of a multilayer filmmay contain more than one polyethylene composition and/or additionalthermoplastics.

Additional embodiments include laminations and coatings, wherein mono ormultilayer films containing the disclosed polyethylene composition areextrusion laminated or adhesively laminated or extrusion coated. Inextrusion lamination or adhesive lamination, two or more substrates arebonded together with a thermoplastic or an adhesive, respectively. Inextrusion coating, a thermoplastic is applied to the surface of asubstrate. These processes are well known to those experienced in theart. Frequently, adhesive lamination or extrusion lamination are used tobond dissimilar materials, non-limiting examples include the bonding ofa paper web to a thermoplastic web, or the bonding of an aluminum foilcontaining web to a thermoplastic web, or the bonding of twothermoplastic webs that are chemically incompatible, e.g. the bonding ofa polyethylene composition containing web to a polyester or polyamideweb. Prior to lamination, the web containing the disclosed polyethylenecomposition(s) may be monolayer or multilayer. Prior to lamination theindividual webs may be surface treated to improve the bonding, anon-limiting example of a surface treatment is corona treating. Aprimary web or film may be laminated on its upper surface, its lowersurface, or both its upper and lower surfaces with a secondary web. Asecondary web and a tertiary web could be laminated to the primary web;wherein the secondary and tertiary webs differ in chemical composition.As non-limiting examples, secondary or tertiary webs may include;polyamide, polyester and polypropylene, or webs containing barrier resinlayers such as EVOH. Such webs may also contain a vapor depositedbarrier layer; for example a thin silicon oxide (SiO_(x)) or aluminumoxide (AlO_(x)) layer. Multilayer webs (or films) may contain three,five, seven, nine, eleven or more layers.

The polyethylene composition disclosed herein can be used in a widerange of manufactured articles including one or more films or filmlayers (monolayer or multilayer). Non-limiting examples of suchmanufactured articles include: food packaging films (fresh and frozenfoods, liquids and granular foods), stand-up pouches, retortablepackaging and bag-in-box packaging; barrier films (oxygen, moisture,aroma, oil, etc.) and modified atmosphere packaging; light and heavyduty shrink films and wraps, collation shrink film, pallet shrink film,shrink bags, shrink bundling and shrink shrouds; light and heavy dutystretch films, hand stretch wrap, machine stretch wrap and stretch hoodfilms; high clarity films; heavy-duty sacks; household wrap, overwrapfilms and sandwich bags; industrial and institutional films, trash bags,can liners, magazine overwrap, newspaper bags, mail bags, sacks andenvelopes, bubble wrap, carpet film, furniture bags, garment bags, coinbags, auto panel films; medical applications such as gowns, draping andsurgical garb; construction films and sheeting, asphalt films,insulation bags, masking film, landscaping film and bags; geomembraneliners for municipal waste disposal and mining applications; batchinclusion bags; agricultural films, mulch film and green house films;in-store packaging, self-service bags, boutique bags, grocery bags,carry-out sacks and t-shirt bags; oriented films, machine direction andbiaxially oriented films and functional film layers in orientedpolypropylene (OPP) films, e.g. sealant and/or toughness layers.Additional manufactured articles including one or more films containingat least one polyethylene composition include laminates and/ormultilayer films; sealants and tie layers in multilayer films andcomposites; laminations with paper; aluminum foil laminates or laminatescontaining vacuum deposited aluminum; polyimide laminates; polyesterlaminates; extrusion coated laminates, and; hot-melt adhesiveformulations. The manufactured articles summarized in this paragraphcontain at least one film (monolayer or multilayer) including at leastone embodiment of the disclosed polyethylene composition.

Desired film physical properties (monolayer or multilayer) typicallydepend on the application of interest. Non-limiting examples ofdesirable film properties include: optical properties (gloss, haze andclarity), dart impact, Elmendorf tear, modulus (1% and 2% secantmodulus), puncture-propagation tear resistance, tensile properties(yield strength, break strength, elongation at break, toughness, etc.)and heat sealing properties (heat seal initiation temperature and hottack strength). Specific hot tack and heat sealing properties aredesired in high speed vertical and horizontal form-fill-seal processesthat load and seal a commercial product (liquid, solid, paste, part,etc.) inside a pouch-like package.

In addition to desired film physical properties, it is desired that thedisclosed polyethylene composition is easy to process on film lines.Those skilled in the art frequently use the term “processability” todifferentiate polymers with improved processability, relative topolymers with inferior processability. A commonly used measure toquantify processability is extrusion pressure; more specifically, apolymer with improved processability has a lower extrusion pressure (ona blown film or a cast film extrusion line) relative to a polymer withinferior processability.

In an embodiment of the disclosure, a film or film layer includes thepolyethylene composition described above.

In embodiments of the disclosure, a film or film layer includes thepolyethylene composition described above and has a thickness of from 0.5to 10 mil.

In embodiments of the disclosure, a film or film layer has a thicknessof from 0.5 to 10 mil.

In embodiments of the disclosure, a film will have a dart impactstrength of 300 g/mil, or 350 g/mil, or 400 g/mil, or 450 g/mil. Inanother embodiment of the disclosure, a film will have a dart impactstrength of from 300 g/mil to 650 g/mil. In a further embodiment of thedisclosure, a film will have dart impact strength of from 350 g/mil to650 g/mil. In a further embodiment of the disclosure, a film will havedart impact strength of from 400 g/mil to 600 g/mil. In yet anotherembodiment of the disclosure, a film will have dart impact strength offrom 400 g/mil to 550 g/mil. In still yet another embodiment of thedisclosure, a film will have dart impact strength of from 400 g/mil to500 g/mil.

In embodiments of the disclosure, a 1 mil film will have a machinedirection (MD) secant modulus at 1% strain of ≥170 MPa, or ≥180 MPa, or≥190 MPa, or ≥200 MPa, or ≥210 MPa, or ≥220 MPa, or ≥230 MPa. In anembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 160 MPa to 280 MPa. In anembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 170 MPa to 280 MPa. In anotherembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 180 MPa to 280 MPa. In anotherembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 190 MPa to 280 MPa. In anotherembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 200 MPa to 270 MPa. In anotherembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 210 MPa to 270 MPa. In anotherembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 220 MPa to 270 MPa. In anotherembodiment of the disclosure, a 1 mil film will have a machine direction(MD) secant modulus at 1% strain of from 230 MPa to 270 MPa.

In an embodiment of the disclosure, a 1 mil film will have a transversedirection (TD) secant modulus at 1% strain of ≥200 MPa, or ≥210 MPa, or≥220 MPa, or ≥230 MPa, or ≥240 MPa, or ≥250 MPa, or ≥260 MPa. In anembodiment of the disclosure, a 1 mil film will have a transversedirection (TD) secant modulus at 1% strain of from 200 MPa to 400 MPa.In another embodiment of the disclosure, a 1 mil film will have atransverse direction (TD) secant modulus at 1% strain of from 210 MPa to400 MPa. In another embodiment of the disclosure, a 1 mil film will havea transverse direction (TD) secant modulus at 1% strain of from 220 MPato 350 MPa. In another embodiment of the disclosure, a 1 mil film willhave a transverse direction (TD) secant modulus at 1 strain of from 230MPa to 350 MPa. In another embodiment of the disclosure, a 1 mil filmwill have a transverse direction (TD) secant modulus at 1% strain offrom 240 MPa to 350 MPa. In another embodiment of the disclosure, a 1mil film will have a transverse direction (TD) secant modulus at 1%strain of from 250 MPa to 350 MPa. In another embodiment of thedisclosure, a 1 mil film will have a transverse direction (TD) secantmodulus at 1% strain of from 250 MPa to 325 MPa.

In embodiments of the disclosure, a 1 mil film will have a machinedirection (MD) tensile strength at break of ≥40 MPa, or ≥45 MPa, or ≥50MPa, or ≥55 MPa. In an embodiment of the disclosure, a 1 mil film willhave a machine direction tensile strength at break of from 30 MPa to 70MPa. In an embodiment of the disclosure, a 1 mil film will have amachine direction (MD) tensile strength at break of from 35 MPa to 70MPa. In another embodiment of the disclosure, a 1 mil film will have amachine direction (MD) tensile strength at break of from 40 MPa to 70MPa. In another embodiment of the disclosure, a 1 mil film will have amachine direction (MD) tensile strength at break of from 50 MPa to 65MPa.

In embodiments of the disclosure, a film will have a machine direction(MD) tear strength of ≥300 g/mil, or ≥325 g/mil, or ≥350 g/mil, or ≥375g/mil, or ≥400 g/mil. In an embodiment of the disclosure, a film willhave a machine direction (MD) tear strength of from 300 g/mil to 550g/mil. In an embodiment of the disclosure, a film will have a machinedirection (MD) tear strength of from 350 g/mil to 500 g/mil. In anembodiment of the disclosure, a film will have a machine direction (MD)tear strength of from 375 g/mil to 475 g/mil. In an embodiment of thedisclosure, a film will have a machine direction (MD) tear strength offrom 400 g/mil to 450 g/mil.

In embodiments of the disclosure, a 1 mil film will have an ASTMpuncture resistance value of ≥70 J/mm, or ≥80 J/mm, or ≥85 J/mm, or ≥90J/mm. In embodiments of the disclosure, a 1 mil film will have an ASTMpuncture value of from 65 J/mm to 110 J/mm, or from 70 J/mm to 105 J/mm,or from 80 J/mm to 100 J/mm.

In embodiments of the disclosure, a 1 mil film will have a haze of ≤16%,or ≤15%, ≤14%, or ≤13%, or ≤12%, or ≤11%. In embodiments of thedisclosure, a 1 mil film will have a haze of from 5% to 20%, of from 6%to 16%, or from 7% to 14%.

In embodiments of the disclosure, a 2 mil film will have a sealinitiation temperature (SIT) of ≤100° C., or ≤95° C., or ≤90° C., or≤85° C., or ≤80° C. In an embodiment of the disclosure, a 2 mil filmwill have a seal initiation temperature (SIT) of between 65° C. and 100°C. In an embodiment of the disclosure, a 2 mil film will have a sealinitiation temperature (SIT) of between 65° C. and 95° C. In anembodiment of the disclosure, a 2 mil film will have a seal initiationtemperature (SIT) of between 70° C. and 90° C. In an embodiment of thedisclosure, a 2 mil film will have a seal initiation temperature (SIT)of between 70° C. and 85° C. In an embodiment of the disclosure, a 2 milfilm will have a seal initiation temperature (SIT) of between 70° C. and80° C.

In an embodiment of the disclosure, a 1 mil film will have an oxygentransmission rate (OTR) of ≥600 cm³ per 100 inch². In an embodiment ofthe disclosure, a 1 mil film will have an oxygen transmission rate (OTR)of ≥625 cm³ per 100 inch². In an embodiment of the disclosure, a 1 milfilm will have an oxygen transmission rate (OTR) of ≥650 cm³ per 100inch². In an embodiment of the disclosure, a 1 mil film will have anoxygen transmission rate (OTR) of ≥675 cm³ per 100 inch². In anembodiment of the disclosure, a 1 mil film will have an oxygentransmission rate (OTR) of ≥700 cm³ per 100 inch². In an embodiment ofthe disclosure, a 1 mil film will have an oxygen transmission rate (OTR)of from 600 to 800 cm³ per 100 inch². In an embodiment of thedisclosure, a 1 mil film will have an oxygen transmission rate (OTR) offrom 650 to 800 cm³ per 100 inch². In an embodiment of the disclosure, a1 mil film will have an oxygen transmission rate (OTR) of from 650 to750 cm³ per 100 inch².

In an embodiment of the disclosure, a 2 mil film will have an area ofhot tack window (AHTW) of ≥170 Newtons·° C. In an embodiment of thedisclosure, a 2 mil film will have an area of hot tack window (AHTW) of200 Newtons·° C. In an embodiment of the disclosure, a 2 mil film willhave an area of hot tack window (AHTW) of ≥210 Newtons·° C. In anembodiment of the disclosure, a 2 mil film will have an area of hot tackwindow (AHTW) of ≥220 Newtons·° C. In an embodiment of the disclosure, a2 mil film will have an area of hot tack window (AHTW) of ≥230 Newtons·°C. In an embodiment of the disclosure, a 2 mil film will have an area ofhot tack window (AHTW) of ≥240 Newtons·° C. In an embodiment of thedisclosure, a 2 mil film will have an area of hot tack window (AHTW) offrom 200 to 320 Newtons·° C. In an embodiment of the disclosure, a 2 milfilm will have an area of hot tack window (AHTW) of from 210 to 300Newtons·° C. In an embodiment of the disclosure, a 2 mil film will havean area of hot tack window (AHTW) of from 220 to 290 Newtons·° C. In anembodiment of the disclosure, a 2 mil film will have an area of hot tackwindow (AHTW) of from 230 to 280 Newtons·° C. In an embodiment of thedisclosure, a 2 mil film will have an area of hot tack window (AHTW) offrom 240 to 280 Newtons·° C.

Some embodiments of the present disclosure provide films withimprovements in machine direction (MD) modulus (1% and/or 2%) and sealinitiation temperature relative to films formed from comparativepolyethylene. Hence, in an embodiment of the disclosure, a film layerhaving a thickness of from 0.5 to 10 mil, has a machine direction (MD)1% secant modulus of ≥200 MPa when measured at a film thickness of about1 mil and a seal initiation temperature (SIT) of ≤95° C. when measuredat a film thickness of about 2 mil. In another embodiment of thedisclosure, a film layer having a thickness of from 0.5 to 10 mil, has amachine direction (MD) 1% secant modulus of ≥210 MPa when measured at afilm thickness of about 1 mil and a seal initiation temperature (SIT) of≤90° C. when measured at a film thickness of about 2 mil. In anotherembodiment of the disclosure, a film layer having a thickness of from0.5 to 10 mil, has a machine direction (MD) 1% secant modulus of ≥220MPa when measured at a film thickness of about 1 mil and a sealinitiation temperature (SIT) of ≤85° C. when measured at a filmthickness of about 2 mil. In another embodiment of the disclosure, afilm layer having a thickness of from 0.5 to 10 mil, has a machinedirection (MD) 1% secant modulus of ≥220 MPa when measured at a filmthickness of about 1 mil and a seal initiation temperature (SIT) of ≤80°C. when measured at a film thickness of about 2 mil.

Some embodiments of the present disclosure provide films withimprovements in machine direction (MD) modulus (1% and/or 2%) and oxygentransmission rates (OTRs) relative to films formed from comparativepolyethylene. Hence, in an embodiment of the disclosure, a film layerhaving a thickness of from 0.5 to 10 mil, has a machine direction (MD)1% secant modulus of ≥200 MPa when measured at a film thickness of about1 mil and an oxygen transmission rate (OTR) of ≥600 cm³ per 100 inch²when measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, the films manufactured using thepolyethylene compositions will have good hot tack performance. Good hottack performance is generally associated with good film performance inbag or pouch packaging lines, such as vertical-form-fill-seal (VFFS)applications lines. Without wishing to be bound by theory, in the hottack profile (seal temperature vs. force), good hot tack performance isindicated by an early (or low) hot tack initiation temperature, then arelatively high force over a wide range of seal temperatures.

Some embodiments of the present disclosure provide films withimprovements in machine direction (MD) modulus (1% and/or 2%) and areaof hot tack window (AHTW) relative to films formed from comparativepolyethylene. Hence, in an embodiment of the disclosure, a film layerhaving a thickness of from 0.5 to 10 mil, has a machine direction (MD)1% secant modulus of ≥200 MPa when measured at a film thickness of about1 mil and an area of hot tack window (AHTW) of ≥220 Newtons·° C. whenmeasured at a film thickness of about 2 mil.

Some embodiments of the present disclosure provide films withimprovements in machine direction (MD) modulus (1% and/or 2%) and sealinitiation temperature relative to films formed from comparativepolyethylene. Hence, in an embodiment of the disclosure, a film layerhaving a thickness of from 0.5 to 10 mil, has a machine direction (MD)1% secant modulus of ≥200 MPa when measured at a film thickness of about1 mil and a seal initiation temperature (SIT) of ≤85° C. when measuredat a film thickness of about 2 mil.

Some embodiments of the present disclosure provide films withimprovements in machine direction (MD) modulus (1% and/or 2%), oxygentransmission rates, seal initiation temperature and area of hot tackwindow (AHTW) relative to films formed from comparative polyethylene.Hence, in an embodiment of the disclosure, a film layer having athickness of from 0.5 to 10 mil, has a has a machine direction (MD) 1%secant modulus of ≥200 MPa when measured at a film thickness of about 1mil, an oxygen transmission rate (OTR) of ≥600 cm³ per 100 inch² whenmeasured at a film thickness of about 1 mil, a seal initiationtemperature (SIT) of ≤85° C. when measured at a film thickness of about2 mil, and an area of hot tack window (AHTW) of ≥220 Newtons·° C. whenmeasured at a film thickness of about 2 mil.

In an embodiment of the disclosure, film satisfies the followingrelationship: area of hot tack window (AHTW)>−2.0981 (machine direction(MD) 1% secant modulus)+564.28; where the AHTW is measured at a filmthickness of about 2 mil, and the machine direction (MD) 1% secantmodulus is measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, film satisfies the followingrelationship: oxygen transmission rate (OTR)>−5.4297 (machine direction(MD) 1% secant modulus)+1767.8; where the OTR is measured at a filmthickness of about 1 mil, and the machine direction (MD) 1% secantmodulus is measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, film satisfies the followingrelationship: seal initiation temperature (SIT)<0.366 (machine direction(MD) 1% secant modulus)+22.509; where the SIT is measured at a filmthickness of about 2 mil, and the machine direction (MD) 1% secantmodulus is measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, film satisfies the followingrelationships: area of hot tack window (AHTW)>−2.0981 (machine direction(MD) 1% secant modulus)+564.28; where the AHTW is measured at a filmthickness of about 2 mil, and the machine direction (MD) 1% secantmodulus is measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, film satisfies the followingrelationship: oxygen transmission rate (OTR)>−5.4297 (machine direction(MD) 1% secant modulus)+1767.8; where the OTR is measured at a filmthickness of about 1 mil, and the machine direction (MD) 1% secantmodulus is measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, film satisfies each of the followingrelationships: i) area of hot tack window (AHTW)>−2.0981 (machinedirection (MD) 1% secant modulus)+564.28, where the AHTW is measured ata film thickness of about 2 mil, and the machine direction (MD) 1%secant modulus is measured at a film thickness of about 1 mil; ii)oxygen transmission rate (OTR)>−5.4297 (machine direction (MD) 1% secantmodulus)+1767.8, where the OTR is measured at a film thickness of about1 mil, and the machine direction (MD) 1% secant modulus is measured at afilm thickness of about 1 mil; and iii) seal initiation temperature(SIT) <0.366 (machine direction (MD) 1% secant modulus)+22.509, wherethe SIT is measured at a film thickness of about 2 mil, and the machinedirection (MD) 1% secant modulus is measured at a film thickness ofabout 1 mil.

In an embodiment of the disclosure, a film layer having a thickness offrom 0.5 to 10 mil, satisfies at least one of the followingrelationships: i) area of hot tack window (AHTW)−2.0981 (machinedirection (MD) 1% secant modulus)+564.28, where the AHTW is measured ata film thickness of about 2 mil, and the machine direction (MD) 1%secant modulus is measured at a film thickness of about 1 mil; ii)oxygen transmission rate (OTR)>−5.4297 (machine direction (MD) 1% secantmodulus)+1767.8, where the OTR is measured at a film thickness of about1 mil, and the machine direction (MD) 1% secant modulus is measured at afilm thickness of about 1 mil; and iii) seal initiation temperature(SIT)<0.366 (machine direction (MD) 1% secant modulus)+22.509, where theSIT is measured at a film thickness of about 2 mil, and the machinedirection (MD) 1% secant modulus is measured at a film thickness ofabout 1 mil.

In an embodiment of the disclosure, a film layer having a thickness offrom 0.5 to 10 mil, satisfies each of the following relationships: i)area of hot tack window (AHTW)>−2.0981 (machine direction (MD) 1% secantmodulus)+564.28, where the AHTW is measured at a film thickness of about2 mil, and the machine direction (MD) 1% secant modulus is measured at afilm thickness of about 1 mil; ii) oxygen transmission rate(OTR)>−5.4297 (machine direction (MD) 1% secant modulus)+1767.8, wherethe OTR is measured at a film thickness of about 1 mil, and the machinedirection (MD) 1 secant modulus is measured at a film thickness of about1 mil; and iii) seal initiation temperature (SIT)<0.366 (machinedirection (MD) 1% secant modulus)+22.509, where the SIT is measured at afilm thickness of about 2 mil, and the machine direction (MD) 1% secantmodulus is measured at a film thickness of about 1 mil.

The films used in the manufactured articles described in this sectionmay optionally include, depending on its intended use, additives andadjuvants. Non-limiting examples of additives and adjuvants include,anti-blocking agents, antioxidants, heat stabilizers, slip agents,processing aids, anti-static additives, colorants, dyes, fillermaterials, light stabilizers, light absorbers, lubricants, pigments,plasticizers, nucleating agents and combinations thereof.

The following examples are presented for the purpose of illustratingselected embodiments of this disclosure; it being understood, that theexamples presented do not limit the claims presented.

EXAMPLES Test Methods

Prior to testing, each specimen was conditioned for at least 24 hours at23±2° C. and 50±10% relative humidity and subsequent testing wasconducted at 23±2° C. and 50±10% relative humidity. Herein, the term“ASTM conditions” refers to a laboratory that is maintained at 23±2° C.and 50±10% relative humidity; and specimens to be tested wereconditioned for at least 24 hours in this laboratory prior to testing.ASTM refers to the American Society for Testing and Materials.

Density was determined using ASTM D792-13 (Nov. 1, 2013).

Melt index was determined using ASTM D1238 (Aug. 1, 2013). Melt indexes,I₂, I₆, I₁₀ and I₂₁ were measured at 190° C., using weights of 2.16 kg,6.48 kg, 10 kg and a 21.6 kg respectively. Herein, the term “stressexponent” or its acronym “S. Ex.”, is defined by the followingrelationship: S.Ex.=log (I₆/I₂)/log(6480/2160); wherein I₆ and I₂ arethe melt flow rates measured at 190° C. using 6.48 kg and 2.16 kg loads,respectively.

M_(n), M_(w), and M_(z) (g/mol) were determined by high temperature GelPermeation Chromatography (GPC) with differential refractive index (DRI)detection using universal calibration (e.g. ASTM-D6474-99). GPC data wasobtained using an instrument sold under the trade name “Waters 150c”,with 1,2,4-trichlorobenzene as the mobile phase at 140° C. The sampleswere prepared by dissolving the polymer in this solvent and were runwithout filtration. Molecular weights are expressed as polyethyleneequivalents with a relative standard deviation of 2.9% for the numberaverage molecular weight (“Mn”) and 5.0% for the weight averagemolecular weight (“Mw”). The molecular weight distribution (MWD) is theweight average molecular weight divided by the number average molecularweight, M_(W)/M_(n). The z-average molecular weight distribution isM_(z)/M_(n). Polymer sample solutions (1 to 2 mg/m L) were prepared byheating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on awheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high-temperature chromatography unit equipped with fourShodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobilephase with a flow rate of 1.0 mL/minute, with a differential refractiveindex (DRI) as the concentration detector. BHT was added to the mobilephase at a concentration of 250 ppm to protect the columns fromoxidative degradation. The sample injection volume was 200 mL. The rawdata were processed with Cirrus GPC software. The columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474.

The short chain branch frequency (e.g. the short chain branching perthousand backbone carbon atoms, or the SCB/1000C) of ethylene copolymersamples was determined by Fourier Transform Infrared Spectroscopy (FTIR)as per the ASTM D6645-01 method. A Thermo-Nicolet 750 Magna-IRSpectrophotometer equipped with OMNIC version 7.2a software was used forthe measurements. Unsaturations in the polyethylene composition werealso determined by Fourier Transform Infrared Spectroscopy (FTIR) as perASTM D3124-98.

High temperature GPC equipped with an online FTIR detector (GPC-FTIR)was used to measure the comonomer content as the function of molecularweight.

Crystallization Elution Fractionation (CEF): A polymer sample (20 to 25mg) was weighed into the sample vial and loaded onto the auto-sampler ofthe Polymer CEF unit. The vail was filled with 6 to 7 ml1,2,4-trichlorobenzene (TCB), heated to the desired dissolutiontemperature (e.g. 160° C.) with a shaking rate of level number 3 for 2hours. The solution (0.5 ml) was then loaded into the CEF columns (twoCEF columns purchased from Polymer Char and installed in series). Afterallowed to equilibrate at a given stabilization temperature (e.g. 115°C.) for 5 minutes, the polymer solution was allowed to crystallize witha temperature drop from the stabilization temperature to 30° C. Afterequilibrating at 30° C. for 10 minutes, the soluble fraction was elutedat 30° C. for 10 minutes, followed by the crystallized sample elutedwith TCB with a temperature ramp from 30° C. to 110° C. The CEF columnswere cleaned at the end of the run for 5 minutes at 150° C. The otherCEF run conditions were as follows: cooling rate 0.5° C./minute, flowrate in crystallization 0.02 mL/minute, heating rate 1.0° C./minute andflow rate in elution 2.0 mL/minute. The data were processed using Excelspreadsheet. The “CDBI₅₀” is defined as the weight percent of ethylenepolymer whose composition is within 50% of the median comonomercomposition (50% on each side of the median comonomer composition). The“CDBI₅₀” may be calculated from the composition distribution curve,determined by the CEF procedure described above, and the normalizedcumulative integral of the composition distribution curve, asillustrated in U.S. Pat. No. 5,376,439 or WO 93/03093.

The “Composition Distribution Branching Index” or “CDBI” mayalternatively by determined using a crystal-TREF unit commerciallyavailable form Polymer ChAR (Valencia, Spain). The acronym “TREF” refersto Temperature Rising Elution Fractionation. A sample of thepolyethylene composition (80 to 100 mg) was placed in the reactor of thePolymer ChAR crystal-TREF unit, the reactor was filled with 35 ml of1,2,4-trichlorobenzene (TCB), heated to 150° C. and held at thistemperature for 2 hours to dissolve the sample. An aliquot of the TCBsolution (1.5 mL) was then loaded into the Polymer ChAR TREF columnfilled with stainless steel beads and the column was equilibrated for 45minutes at 110° C. The polyethylene composition was then crystallizedfrom the TCB solution, in the TREF column, by slowly cooling the columnfrom 110° C. to 30° C. using a cooling rate of 0.09° C. per minute. TheTREF column was then equilibrated at 30° C. for 30 minutes. Thecrystallized polyethylene composition was then eluted from the TREFcolumn by passing pure TCB solvent through the column at a flow rate of0.75 mL/minute as the temperature of the column was slowly increasedfrom 30° C. to 120° C. using a heating rate of 0.25° C. per minute.Using Polymer ChAR software a TREF distribution curve was generated asthe polyethylene composition was eluted from the TREF column, i.e. aTREF distribution curve is a plot of the quantity (or intensity) ofpolyethylene composition eluting from the column as a function of TREFelution temperature. A CDB 150 may be calculated from the TREFdistribution curve for each polyethylene composition analyzed. The“CDBI₅₀” is defined as the weight percent of ethylene polymer whosecomposition is within 50% of the median comonomer composition (50% oneach side of the median comonomer composition); it is calculated fromthe TREF composition distribution curve and the normalized cumulativeintegral of the TREF composition distribution curve. Those skilled inthe art will understand that a calibration curve is required to converta TREF elution temperature to comonomer content, i.e. the amount ofcomonomer in the polyethylene composition fraction that elutes at aspecific temperature. The generation of such calibration curves aredescribed in references such as Wild, et al., J. Polym. Sci., Part B,Polym. Phys., Vol. 20 (3), pages 441-455: hereby fully incorporated byreference. Note: The “CDBI₂₅” is defined as the weight percent ofpolyethylene composition whose composition is within 25% of the mediancomonomer composition (25% on each side of the median comonomercomposition).

Dynamic mechanical analyses were carried out with a rheometer, namelyRheometrics Dynamic Spectrometer (RDS-II) or Rheometrics SR5 or ATSStresstech, on compression molded samples under nitrogen atmosphere at190° C., using 25 mm diameter cone and plate geometry. The oscillatoryshear experiments were done within the linear viscoelastic range ofstrain (10% strain) at frequencies from 0.05 to 100 rad/s. The values ofstorage modulus (G′), loss modulus (G″), complex modulus (G*) andcomplex viscosity (η*) were obtained as a function of frequency. Thesame rheological data can also be obtained by using a 25 mm diameterparallel plate geometry at 190° C. under nitrogen atmosphere. The Zeroshear viscosity is estimated using the Ellis model, i.e.η(ω)=η_(0z)/(1+τ/τ_(1/2))^(α−1), where no is the zero shear viscosity.τ_(1/2) is the value of the shear stress at which η=η₀/2 and α is one ofthe adjustable parameters. The Cox-Merz rule is assumed to be applicablein the present disclosure.

The DRI, is the “dow rheology index”, is defined by the equation:DRI=[365000(τ₀/η₀)−1]/10; wherein τ₀ is the characteristic relaxationtime of the polyethylene and no is the zero shear viscosity of thematerial. The DRI is calculated by least squares fit of the rheologicalcurve (dynamic complex viscosity versus applied frequency eg. 0.01-100rads/s) as described in U.S. Pat. No. 6,114,486 with the followinggeneralized Cross equation, i.e. η(ω)=η₀/[1+(ωτ₀)^(n)]; wherein n is thepower law index of the material, η(ω) and ω are the measured complexviscosity and applied frequency data respectively. When determining theDRI, the zero shear viscosity, no used was estimated with the Ellismodel, rather than the Cross model.

The crossover frequency is the frequency at which storage modulus (G′)and loss modulus (G″) curves cross with each other, while G′@G″=500 Pais the storage modulus at which the loss modulus (G″) is at 500 Pa.

Primary melting peak (° C.), melting peak temperatures (° C.), heat offusion (J/g) and crystallinity (%) was determined using differentialscanning calorimetry (DSC) as follows: the instrument was firstcalibrated with indium; after the calibration, a polymer specimen isequilibrated at 0° C. and then the temperature was increased to 200° C.at a heating rate of 10° C./min; the melt was then kept isothermally at200° C. for five minutes; the melt was then cooled to 0° C. at a coolingrate of 10° C./min and kept at 0° C. for five minutes; the specimen wasthen heated to 200° C. at a heating rate of 10° C./min. The DSC Tm, heatof fusion and crystallinity are reported from the 2^(nd) heating cycle.

Film dart impact strength was determined using ASTM D1709-09 Method A(May 1, 2009). In this disclosure the dart impact test employed a 1.5inch (38 mm) diameter 8hemispherical headed dart.

The film “ASTM puncture” is the energy (J/mm) required to break the filmwas determined using ASTM D5748-95 (originally adopted in 1995,reapproved in 2012). The puncture test is performed on a mechanicaltester, in which the puncture probe is attached to the load cell whichis mounted on a moving crosshead. The film is clamped into a clampingmechanism which has a 4 inch (102 mm) diameter opening. The clampingmechanism is attached to a fixed plate. The cross head speed is set at10 in/min (255 mm/min). The maximum force and energy to puncture thefilm are recorded.

The “slow puncture” or “lubricated puncture” test was performed asfollows: the energy (J/mm) to puncture a film sample was determinedusing a 0.75-inch (1.9-cm) diameter pear-shaped fluorocarbon coatedprobe travelling at 10-inch per minute (25.4-cm/minute). ASTM conditionswere employed. Prior to testing the specimens, the probe head wasmanually lubricated with Muko Lubricating Jelly to reduce friction. MukoLubricating Jelly is a water-soluble personal lubricant available fromCardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. Theprobe was mounted in an Instron Model 5 SL Universal Testing Machine anda 1000-N load cell as used. Film samples (1.0 mil (25 μm) thick, 5.5inch (14 cm) wide and 6 inch (15 cm) long) were mounted in the Instronand punctured. The following film tensile properties were determinedusing ASTM D882-12 (Aug. 1, 2012): tensile break strength (MPa),elongation at break (%), tensile yield strength (MPa), tensileelongation at yield (%) and film toughness or total energy to break(ft·lb/in³). Tensile properties were measured in the both the machinedirection (MD) and the transverse direction (TD) of the blown films.

The secant modulus is a measure of film stiffness. The secant modulus isthe slope of a line drawn between two points on the stress-strain curve,i.e. the secant line. The first point on the stress-strain curve is theorigin, i.e. the point that corresponds to the origin (the point of zeropercent strain and zero stress), and; the second point on thestress-strain curve is the point that corresponds to a strain of 1%;given these two points the 1% secant modulus is calculated and isexpressed in terms of force per unit area (MPa). The 2% secant modulusis calculated similarly. This method is used to calculated film modulusbecause the stress-strain relationship of polyethylene does not followHook's law; i.e. the stress-strain behavior of polyethylene isnon-linear due to its viscoelastic nature. Secant moduli were measuredusing a conventional Instron tensile tester equipped with a 200 lbf loadcell. Strips of monolayer film samples were cut for testing withfollowing dimensions: 14 inch long, 1 inch wide and 1 mil thick;ensuring that there were no nicks or cuts on the edges of the samples.Film samples were cut in both the machine direction (MD) and thetransverse direction (TD) and tested. ASTM conditions were used tocondition the samples. The thickness of each film was accuratelymeasured with a hand-held micrometer and entered along with the samplename into the Instron software. Samples were loaded in the Instron witha grip separation of 10 inch and pulled at a rate of 1 inch/mingenerating the strain-strain curve. The 1% and 2% secant modulus werecalculated using the Instron software.

The oxygen transmission rate (OTR) of the blown film was tested using anOxtran 2/20 instrument manufactured by MOCON Inc, Minneapolis, Minn.,USA. The instrument has two test cells (A and B) and each film samplewas analyzed in duplicate. The OTR result reported is the average of theresults from these two test cells (A and B). The test is carried out ata temperature of 23° C. and at a relative humidity of 0%. The filmsample area used for testing was 100 cm². The carrier gas used was 2%hydrogen gas in a balance of nitrogen gas and the test gas is ultra highpurity oxygen. The blown films which were tested each had a filmthickness of 1 mil.

Puncture-propagation tear resistance of blown film was determined usingASTM D2582-09 (May 1, 2009). This test measures the resistance of ablown film to snagging, or more precisely, to dynamic puncture andpropagation of that puncture resulting in a tear. Puncture-propagationtear resistance was measured in the machine direction (MD) and thetransverse direction (TD) of the blown films.

Film tear performance was determined by ASTM D1922-09 (May 1, 2009); anequivalent term for tear is “Elmendorf tear”. Film tear was measured inboth the machine direction (MD) and the transverse direction (TD) of theblown films.

Film optical properties were measured as follows: Haze, ASTM D1003-13(Nov. 15, 2013), and; Gloss ASTM D2457-13 (Apr. 1, 2013).

In this disclosure, the “Hot Tack Test” was performed as follows, usingASTM conditions. Hot tack data was generated using a J&B Hot Tack Testerwhich is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630Maamechelen, Belgium. In the hot tack test, the strength of a polyolefinto polyolefin seal is measured immediately after heat sealing two filmsamples together (the two film samples were cut from the same roll of2.0 mil (51-μm) thick film), i.e. when the polyolefin macromoleculesthat include the film are in a semi-molten state. This test simulatesthe heat sealing of polyethylene films on high speed automatic packagingmachines, e.g., vertical or horizontal form, fill and seal equipment.The following parameters were used in the J&B Hot Tack Test: filmspecimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; filmsealing pressure, 0.27 N/mm²; delay time, 0.5 second; film peel speed,7.9 in/second (200 mm/second); testing temperature range, 131° F. to293° F. (55° C. to 145° C.); temperature increments, 9° F. (5° C.); andfive film samples were tested at each temperature increment to calculateaverage values at each temperature. In this way, a hot tack profile ofpulling force vs sealing temperature is generated. The following datacan be calculated from this hot tack profile: the “Tack Onset@1.0 N (°C.)”, is the temperature at which a hot tack force of 1N was observed(an average of five film samples); the “Max Hot tack Strength (N)”, isthe maximum hot tack force observed (an average of five film samples)over the testing temperature range; the “Temperature—Max. Hot tack (°C.)”, is the temperature at which the maximum hot tack force wasobserved. Finally, the area of the hot-tack (strength) window (the “areaof hot tack window” or the “AHTW”) is an estimate of the area under thishot tack profile from the hot-tack on-set temperature to the temperatureimmediately prior to the melting of the specimen. The latter temperatureprior to the melting of the specimen is typically at 130° C., but notnecessarily at 130° C. Piece-wise regressions (linear or polynomial)were performed for different segments of the hot tack profile to obtainthe mathematical relationships between seal temperature and pullingforce. The partial area of each temperature-force segment was thencalculated. The total area (AHTW) is the summation of each partial areaof each segment of the hot tack profile within the specified range(i.e., from the hot-tack on-set temperature to the temperatureimmediately prior to the melting of the specimen).

In this disclosure, the “Heat Seal Strength Test” (also known as “thecold seal test”) was performed as follows. ASTM conditions wereemployed. Heat seal data was generated using a conventional InstronTensile Tester. In this test, two film samples are sealed over a rangeof temperatures (the two film samples were cut from the same roll of 2.0mil (51-μm) thick film). The following parameters were used in the HeatSeal Strength (or cold seal) Test: film specimen width, 1 inch (25.4mm); film sealing time, 0.5 second; film sealing pressure, 40 psi (0.28N/mm²); temperature range, 212° F. to 302° F. (100° C. to 150° C.) andtemperature increment, 9° F. (5° C.). After aging for at least 24 hoursat ASTM conditions, seal strength was determined using the followingtensile parameters: pull (crosshead) speed, 12 inch/min (2.54 cm/min);direction of pull, 90° to seal, and; 5 samples of film were tested ateach temperature increment. The Seal Initiation Temperature, hereafterS.I.T., is defined as the temperature required to form a commerciallyviable seal; a commercially viable seal has a seal strength of 2.0 lbper inch of seal (8.8 N per 25.4 mm of seal).

The hexane extractable content of a polymer sample was determinedaccording to the Code of Federal Registration 21 CFR § 177.1520 Para (c)3.1 and 3.2; wherein the quantity of hexane extractable material in afilm is determined gravimetrically. Elaborating, 2.5 grams of 3.5 mil(89 μm) monolayer film was placed in a stainless steel basket, the filmand basket were weighed (w′), while in the basket the film was:extracted with n-hexane at 49.5° C. for two hours; dried at 80° C. in avacuum oven for 2 hours; cooled in a desiccator for 30 minutes, and;weighed (we). The percent loss in weight is the percent hexaneextractable (w^(C6)): w^(C6)=100×(w^(i)−w^(f))/w^(i).

Polyethylene Compositions

A polyethylene composition including a first, second and thirdpolyethylene was made by melt blending polyethylene composition A withpolyethylene B.

Polyethylene composition A was made using a single site catalyst systemin a dual parallel reactor solution polymerization process. As a result,polyethylene composition A included a first polyethylene made with asingle site catalyst and a second polyethylene made with a single sitecatalyst. A parallel mode solution phase polymerization reactor process,has been described in US. Pat. Appl. No. 15/491,264 (co-pending with thepresent application). Basically, in parallel mode the exit streamsexiting each of a first reactor (R1) and a second reactor (R2) arecombined downstream of each reactor and the polymer product is obtainedafter devolatilization.

The following examples illustrate the continuous solutioncopolymerization of ethylene and 1-octene at medium pressure in a dualreactor system connected in parallel. The first and second reactorpressure was about 16,000 kPa (about 2.3×10³ psi). The first reactor wasoperated at a lower temperature than the second reactor. The firstreactor had a volume of 12 liters and the second reactor had a volume of24 liters. Both reactors were agitated to ensure good mixing of thereactor contents. The process was continuous in all feed streams (i.e.solvents, which were methyl pentane and xylene; monomers and catalystand cocatalyst components) and in the removal of product. Monomer(ethylene) and comonomer (1-octene) were purified prior to addition tothe reactor using conventional feed preparation systems (such as contactwith various absorption media to remove impurities such as water, oxygenand polar contaminants). The reactor feeds were pumped to the reactorsat the ratios shown in Table 1. Average residence times for the reactorsare calculated by dividing average flow rates by reactor volume. Theresidence time in each reactor for all of the inventive experiments wasless than 10 minutes and the reactors were well mixed. The catalystdeactivator used was octanoic acid (caprylic acid), commerciallyavailable from P&G Chemicals, Cincinnati, Ohio, U.S.A.

The following single site catalyst (SSC) components were used to preparethe first polyethylene in a first reactor (R1) configured in parallel toa second reactor (R2): cyclopentadienyl tri(tertiarybutyl)phosphiniminetitanium dichloride [Cp((t-Bu)₃PN)TiCl₂]; methylaluminoxane (MMAO-07);trityl tetrakis(pentafluoro-phenyl)borate (trityl borate), and2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylaluminoxane (MMAO-07) and2,6-di-tert-butyl-4-ethylphenol are premixed in-line and then combinedwith cyclopentadienyl tri(tertiarybutyl)phosphinimine titaniumdichloride [Cp((t-Bu)₃PN)TiCl₂] and trityltetrakis(pentafluoro-phenyl)borate just before entering thepolymerization reactor (R1).

The following single site catalyst (SSC) components were used to preparethe second polyethylene in a second reactor (R2) configured in parallelto a first reactor (R1): cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride [Cp((t-Bu)₃PN)TiCl₂];methylaluminoxane (MMAO-07); trityl tetrakis(pentafluoro-phenyl)borate(trityl borate), and 2,6-di-tert-butyl-4-ethylphenol (BHEB).Methylaluminoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol arepremixed in-line and then combined with cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride [Cp((t-Bu)₃PN)TiCl₂]and trityl tetrakis(pentafluoro-phenyl)borate just before entering thepolymerization reactor (R1).

Polyethylene B, on the other hand is made in a single solutionpolymerization reactor using a single site catalyst, as described above;however, in this example the single site catalyst was fed only to asecond reactor (R2) to prepare polyethylene B in a single reactor. Forthe sake of clarity, polyethylene B becomes the third polyethylenewithin the final polyethylene composition.

Table 1, shows the reactor conditions used to make polyethylenecomposition A, as well as polyethylene B. The properties of polyethylenecomposition A, as well as polyethylene B are shown in Table 2.

TABLE 1 Reactor Operating Conditions Blending Component PE Composition ASSC in R1 and SSC PE B in R2 (dual reactor SSC in R2 Description inparallel mode) (single reactor) Reactor 1 (R1) SSC NA TSR (kg/hr) 434.9NA Ethylene concentration 6.4 NA (wt %) 1-Octene/ethylene in 2.97 NAfresh feed (g/g) Primary feed 35.0 NA temperature (° C.) MeanTemperature (° C.) 120.6 NA Ethylene conversion 90.1 NA Hydrogen Feed(ppm) 0.27 NA Catalyst (ppm) to R1 0.52 NA SSC - Al/Ti (mol/mol) 100 NASSC - BHEB/Al 0.3 NA (mol/mol) SSC - B/Ti (mol/mol) 1.2 NA Reactor 2(R2) SSC SSC TSR (kg/hr) 189.9 650 Ethylene concentration 12.48 11.0 (wt%) 1-Octene/ethylene in 0.0 0.02 fresh feed (g/g) Primary feed 45.0 45.0temperature (° C.) Mean Temperature (° C.) 186.3 175.4 Ethyleneconversion 89.8 89.5 Hydrogen Feed (ppm) 0.9 1.33 Catalyst (ppm) to R20.38 0.12 SSC - Al/Ti (mol/mol) 65 65.0 SSC - BHEB/Al 0.3 0.30 (mol/mol)SSC - B/Ti (mol/mol) 0.9 1.5

TABLE 2 Blend Component Properties Blending Component PE Composition ASSC in R1 and SSC PE B in R2 (dual reactor SSC in R2 Description inparallel mode) (single reactor) Catalysts SSC/SSC SSC Density (g/cm³)0.9088 0.9424 Melt Index I₂ (g/10 min) 0.57 0.77 Melt Index I₆ (g/10min) 2.12 2.91 Melt Index I₁₀ (g/10 min) 3.73 5.06 Melt Index I₂₁ (g/10min) 11.1 13.8 Melt Flow Ratio 19.5 17.9 (I₂₁/I₂) Stress Exponent 1.21.21 Melt Flow Ratio 6.51 6.45 (I₁₀/I₂) Branch Frequency - FTIR BranchFreq/1000C 20.2 0.5 Comonomer 1-octene 1-octene Comonomer 4 0.1 Content(mole %) Comonomer 14.4 0.4 Content (weight %) Internal 0.016 0.009Unsat/100C Side Chain 0 0 Unsat/100C Terminal 0.005 0.008 Unsat/100CGPC - Conventional M_(n) 64993 57692 M_(w) 118812 108937 M_(z) 188868171703 Polydispersity 1.83 1.89 Index (M_(w)/M_(n))

The properties of the polyethylene composition which was obtained frommelt blending polyethylene composition A with polyethylene B (in a ratioof 80 wt % to 20 wt % respectively) are provided in Table 3 as InventiveExample 1. The materials were melt blended using a Coperion ZSK 26co-rotating twin screw extruder with an L/D of 32:1. The extruder wasfitted with an underwater pelletizer and a Gala spin dryer. Thematerials were co-fed to the extruder using gravimetric feeders toachieve the desired ratios of polyethylene composition A to polyethyleneB. The blends were compounded using a screw speed of 200 rpm at anoutput rate of 15-20 kg/hour and at a melt temperature of 225-230° C.

Data for comparative polyethylene compositions, Comparative Examples 1-9is also included in Table 3. Comparative Example 1 is ELITE® 5400G, aresin commercially available from the Dow Chemical Company. ELITE® 5400Ghas a density of about 0.916 g/cm³ and a melt index I₂ of about 1dg/min. Comparative Example 2 is SURPASS® FP117-C, a resin commerciallyavailable from the NOVA Chemicals Corporation. SURPASS® FP117-C has adensity of 0.917 g/cm³ and a melt index I₂ of 1 dg/min. ComparativeExamples 3 and 4 are resins made according to U.S. Pat. Appl. Pub. No.2016/0108221. Comparative Example 3 is an ethylene/1-octene copolymer,has a density of about 0.917 g/cm³, a melt index I₂ of about 0.96dg/min, and is made in a multi reactor solution process in which a firstreactor and a second reactor are configured in series with one another.Comparative Example 4 is an ethylene/1-octene copolymer, has a densityof about 0.913 g/cm³, a melt index I₂ of about 0.85 dg/min, and is madein a multi reactor solution process in which a first reactor and asecond reactor are configured in series with one another. ComparativeExample 5 is SCLAIR® FP112-A, a resin commercially available from theNOVA Chemicals Corporation. SCLAIR® FP112-A has a density of 0.912 g/cm³and a melt index I₂ of 0.9 dg/min. Comparative Example 6 is EXCEED®1018CA, a resin commercially available from ExxonMobil. EXCEED® 1018CAhas a density of about 0.918 g/cm³ and a melt index I₂ of about 0.94dg/min. Comparative Example 7 is MARLEX® D139, a resin commerciallyavailable from ChevronPhillips. MARLEX® D139 has a density of about0.918 g/cm³ and a melt index I₂ of about 0.9 dg/min. Comparative Example8 is SCLAIR® FP120-A, a resin commercially available the NOVA ChemicalsCorporation. FP120-A has a density of 0.920 g/cm³ and a melt index I₂ of1 dg/min. Comparative Example 9 is SCLAIR® FP026-F, a resin commerciallyavailable the NOVA Chemicals Corporation. FP026-F has a density of 0.926g/cm³ and a melt index I₂ of 0.75 dg/min.

TABLE 3 Polyethylene Composition Properties Inventive 1 (80 wt % PEComposition A/ Example No. 20 wt % PE B) Comparative 1 Comp. 2 Comp. 3Comp. 4 Density (g/cm³) 0.9179 0.9159 0.9166 0.9167 0.913 Melt Index I₂0.58 1 0.99 0.96 0.85 (g/10 min) Melt Index I₆ 2.23 4.46 4 3.72 3.09(g/10 min) Melt Index I₁₀ 8.57 7.57 6.65 (g/10 min) Melt Index I₂₁ 11.731.3 29 24.4 (g/10 min) Melt Flow 20.2 31.4 29.4 25.4 21.5 Ratio(I₂₁/I₂) Stress 1.22 1.36 1.27 1.23 1.21 Exponent Melt Flow 8.61 7.677.24 6.78 Ratio (I₁₀/I₂) Rheological Properties Zero Shear 17610 156008688 9433 11350 Viscosity - 190° C. (Pa-s) Crossover 103.88 110.98 73.5681.27 98.88 Frequency - 190° C. (rad/s) DRI 0.344 2.41 0.26 0.23 0.22G′@G″500 Pa= 42.8 79.3 22.8 23.9 32 Branch Frequency - FTIR Branch 17.115.2 14.1 15.6 17.1 Freq/1000C Comonomer 1-octene 1-octene 1-octene1-octene 1-octene Comonomer 3.4 3 2.8 3.1 3.4 Content (mole %) Comonomer12.4 11.2 10.4 11.4 12.7 Content (wt %) Internal 0.015 0.003 0.019 0.0090.007 Unsat/100C Side Chain 0 0.004 0.003 0.006 0.003 Unsat/100CTerminal 0.005 0.029 0.006 0.046 0.027 Unsat/100C CEF Soluble 8.04 2.050.77 3.78 2.42 fraction (%), ≤30° C. High 56.2 24.14 7.22 13.74 19.72temperature fraction % CDBI₅₀ 22.2 66.9 81.6 66.4 70.4 DSC First Melting77.29 101 109 105.7 100.0 Peak (° C.) Second 126.64 118 112 117.4 119.3Melting Peak (° C.) Third Melting 129.86 122 - 121.2 122.8 Peak (° C.)Heat of Fusion 131.12 119 123 123.9 112.6 (J/g) Crystallinity 45.2141.19 42.29 42.72 38.82 (%) GPC - Conventional M_(n) 58229 36781 3393933939 44573 M_(w) 113744 99802 102503 102503 114666 M_(z) 179056 210866234321 234321 262824 Polydispersity 1.95 2.71 3.02 3.02 2.57 Index(M_(w)/M_(n)) Mz/Mw 1.57 2.11 2.29 2.29 2.29 Hexane 0.42 0.54 0.56 0.770.61 Extractables (%) - Plaque Example No. Comp. 5 Comp. 6 Comp. 7 Comp.8 Comp. 9 Density (g/cm³) 0.912 0.919 0.918 0.920 0.926 Melt Index I₂0.9 0.94 0.89 1 0.75 (g/10 min) Melt Index I₆ 3.16 3.14 4.29 3.02 (g/10min) Melt Index I₁₀ 5.16 5.22 — — (g/10 min) Melt Index I₂₁ 14.8 15.229.8 20.1 (g/10 min) Melt Flow 31.4 15.8 17.2 29.8 27 Ratio (I₂₁/I₂)Stress 1.34 1.11 1.15 1.32 1.31 Exponent Melt Flow 5.64 5.94 — — Ratio(I₁₀/I₂) Rheological Properties Zero Shear 12990 7731 9198 10783 14750Viscosity - 190° C. (Pa-s) Crossover 83.76 159.80 149.38 107.5 91.93Frequency - 190° C. (rad/s) DRI 0.01 0.09 — — G′@G″500 Pa= 45.7 8 34.141.9 47.7 Branch Frequency - FTIR Branch 19.2 13.4 13.1 Freq/1000 C.Comonomer 1-octene 1-hexene 1-hexene 1-octene 1-octene Comonomer 3.8 2.72.6 2.6 1.7 Content (mole %) Comonomer 13.8 9.9 9.7 9.7 6.3 Content (wt%) Internal 0.007 0.002 0.006 0.005 0.002 Unsat/100 C. Side Chain 0.0070.004 0.005 0.006 0.004 Unsat/100 C. Terminal 0.045 0.01 0.007 0.0520.048 Unsat/100 C. CEF Soluble 7.13 0.57 0.57 2.85 1.14 fraction (%),≤30° C. High 18.8 21.21 24.81 24.78 36.56 temperature fraction % CDBI₅₀62.5 68.30 78.20 54.10 48.80 DSC First Melting 102.0 109.52 106.26108.93 115.24 Peak (° C.) Second 117.9 118.08 116.62 119.52 121.5Melting Peak (° C.) Third Melting 121.6 — — — Peak (° C.) Heat of Fusion110.6 126.96 125.56 132.95 144.24 (J/g) Crystallinity 38.14 43.78 43.2945.84 49.74 (%) GPC - Conventional M_(n) 33139 55850 55399 31575 35549M_(w) 118358 110641 106175 101954 112255 M_(z) 379353 186289 180670302775 297745 Polydispersity 3.57 1.98 1.92 3.40 3.16 Index(M_(w)/M_(n)) Mz/Mw 3.21 1.68 1.70 2.82 2.65 Hexane 1.40 0.26 0.37 0.440.22 Extractables (%) - Plaque

Details of the Inventive polyethylene composition components: the firstpolyethylene, the second polyethylene, and the third polyethylene, areprovided in Table 4. With the exception of the weight percentages, w1and w2 (which are found by adjusting the de-convoluted values, w1′ andw2′, as is further discussed below) the data in Table 4 includes themathematically de-convoluted component properties of polyethylenecomposition A (which included the first polyethylene which was made witha single site catalyst and the second polyethylene which was made with asingle site catalyst) as well as the experimentally determinedproperties of polyethylene B (the third polyethylene which was made witha single site catalyst). High temperature GPC equipped with an onlineFTIR detector (GPC-FTIR) was used to measure the comonomer content as afunction of molecular weight. In order to de-convolute the polyethylenecomposition A (which results from use of a SSC in R1 and R2 in parallelmode polymerization) into components, the mathematical deconvolutionmodel described in U.S. Pat. No. 8,022,143 was used. The mathematicaldeconvolution of the GPC and GPC-FTIR data, the molecular weightdistribution of the first polyethylene (the SSC component made in R1,one catalyst site) and the second polyethylene (the SSC component madein R2, one catalyst site) was modeled using a single Schultz Florydistribution (where the Mw/Mn was assumed to be 2; the Mn was Mw/2 andthe Mz was 1.5×Mw) as described in U.S. Pat. No 8,022,143. To improvethe deconvolution accuracy and consistency, as a constraint, the meltindex, I₂, of the modeled composition (i.e. the dual-reactorpolyethylene composition A) was set and the following relationship wassatisfied during the deconvolution:

Log₁₀(I₂) = 22.326528 + 0.003467 * [Log₁₀(M_(n))]³ − 4.322582 * Log₁₀(M_(w)) − 0.180061 * [Log₁₀(M_(z))]² + 0.026478 * [Log₁₀(M_(z))]³

where the experimentally measured overall melt index (i.e. ofpolyethylene composition A), I₂, was used on the left side of theequation. Hence, a total of two sites (one for each SSC) were used tode-convolute polyethylene composition A. The w(i) and Mn(i), i=1 to 2,were obtained while Mw(i) and Mz(i) of each site were calculated usingthe above relationships using Mn(i) for each site. During thedeconvolution, the overall M_(n), M_(w) and M_(z) of polyethylenecomposition A was calculated with the following relationships:M_(n)=1/Sum(w_(i)/M_(n)(i)), M_(w)=Sum(w_(i)×M_(w)(i)),M_(z)=Sum(w_(i)×M_(z)(i)²), where i represents the i-th component andw_(i) represents the relative weight fraction of the i-th component inthe composition from the above 2-site deconvolution. The GPC-FTIRchromatograph profile was subsequently deconvoluted using the w(i)results to obtain SCB(i), i=1 to 2.

The Mn, Mw, Mz and SCB/1000C of the first and second polyethylenes madewith a SSC in each of R1 and R2 were then calculated using the aboverelationships, with the above data of Mn(i), Mw(i), Mz(i), SCB(i) foreach catalyst site.

When the polymer made with the single site catalyst in R2 was anethylene homopolymer, as is the case in the present examples, thenduring the deconvolution analysis the SCB/1000C for the modeled SSC sitewas set as zero. If however, the polymer made by the SSC was acopolymer, then the SCB value would be determined for the SSC site usingthe deconvolution model presented above.

In order to calculate the melt index, I₂ of each of the first and secondpolyethylenes in polyethylene composition A, the following melt index,I₂ model was used:

Log₁₀(melt  index, I₂) = 22.326528 + 0.003467 * [Log₁₀(M_(n))]³ − 4.322582 * Log₁₀(M_(w)) − 0.180061 * [Log₁₀(M_(z))]² + 0.026478 * [Log₁₀(M_(z))]³

where the M_(n), M_(w) and M_(z) were the deconvoluted values of thefirst or second polyethylene components present in polyethylenecomposition A, as obtained from the results of the above GPCdeconvolution.

The density of the first polyethylene which was an ethylene copolymermade using a single site catalyst was calculated using the followingdensity model:

density  of  the  first  polyethylene  made  with  a  SSC = 0.979863 − 0.00594808 * (FTIRSCB/1000C)^(0.65) − 0.000383133 * [Log₁₀(M_(n))]³ − 0.00000577986 * (M_(w)/M_(n))³ + 0.00557395 * (M_(z)/M_(w))^(0.25)

where the M_(n), M_(w) and M_(z) were the deconvoluted values of thefirst polyethylene as obtained from the results of the above GPCdeconvolution and the SCB/1000C was obtained from the GPC-FTIRdeconvolution. The density of the second polyethylene which was anethylene homopolymer made with a single site catalyst was determinedusing the same equation used above for finding the density of the firstpolyethylene, but with the value for the short chain branching set tozero to cancel out the corresponding term:

density  of  the  second  polyethylene  made  with  a  SSC = 0.979863 − 0.000383133 * [Log₁₀(M_(n))]³ − 0.00000577986 * (M_(w)/M_(n))³ + 0.00557395 * (M_(z)/M_(w))^(0.25).

The de-convolution provided the density (d1, and d2), melt index (I₂ ¹and I₂ ²), short chain branching (SCB1 with the SCB2 being set as zerofor an ethylene homopolymer) the weight average and number averagemolecular weights (Mw1, Mn1, Mw2 and Mn2), and the weight fraction (w1′and w2′) of the first and second polyethylenes The resultingdeconvoluted properties as well as the relative weight percentages w1,w2 (which for the first and the second polyethylenes, respectively, arefound by modifying the deconvoluted weight fractions w1′ and w2′ tomatch the amount of polyethylene composition A in the final melt blendedpolyethylene composition, as determined by the blending rules discussedfurther below) are provided in Table 4.

The following basic blending rules were used to achieve the desiredpolyethylene compositions including a first, a second and a thirdpolyethylene:

w1=weight percentage of the first polyethylene in the final polyethylenecomposition;

w2=weight percentage of the second polyethylene in the finalpolyethylene composition;

w3=weight percentage of the third polyethylene in the final polyethylenecomposition;

w1*=weight percentage of polyethylene composition A in the melt blend;

w2*=weight percentage of polyethylene B in the melt blend;

w1′=weight percentage of the first polyethylene in polyethylenecomposition A (i.e. the w1′ determined from the mathematicaldeconvolution of polyethylene composition A);

w2′=weight percentage of the second polyethylene in polyethylenecomposition A (i.e. the w2′ determined from the mathematicaldeconvolution of polyethylene composition A);

where,

-   -   w1+w2+w3=1;    -   w1*+w2*=1; and    -   w1′+w2′=1;

so that,

-   -   w1=w1*×w1′;    -   w2=w1*×w2′; and    -   w3=w2*.

TABLE 4 Polyethylene Composition Component Properties Inventive PEExample No. Composition 1 Polyethylene Composition Density (g/cm³)0.9179 I₂ (dg/min) 0.58 Stress Exponent 1.22 MFR (I₂₁/I₂) 20.2 Mn 58229Mw 113744 Mz 179056 Mw/Mn 1.95 Mz/Mw 1.57 The First PolyethyleneCatalyst Type 1 Single Site Catalyst weight fraction, w1 0.560 (note:w1′ = 0.700 from deconvolution) Mn1 57700 Mw1 115400 Mw1/Mn1 2 (Mw1/ Mn1< 2.3) short chain branches per 29.6 1000 carbons I₂ ¹ (g/10 min.) 0.48d1 (g/cm³) 0.8909 The Second Polyethylene Catalyst Type 2 Single SiteCatalyst weight fraction, w2 0.240 (note: w2′ = 0.300 fromdeconvolution) Mn2 49550 Mw2 99100 Mw2/Mn2 2 (Mw2/ Mn2 < 2.3) shortchain branches per 0 1000 carbons I₂ ² (g/10 min) 0.86 d2 (g/cm³) 0.9463The Third Polyethylene Catalyst Type 3 Single Site Catalyst weightfraction, w3 0.200 Mn3 57692 Mw3 108937 Mw3/Mn3 1.89 (Mw3/ Mn3 < 2.3)short chain branches per 0.5 1000 carbons I₂ ³ (g/10 min) 0.77 d3(g/cm³) 0.9424

With reference to FIG. 1, a person skilled in the art will recognizethat the inventive polyethylene composition has a unimodal GPC profile.

With reference to FIGS. 2, a person skilled in the art will recognizethat the inventive polyethylene composition has a partially reversecomonomer incorporation, where the comonomer incorporation first risesas molecular weight increases, and then falls as the molecular weightincreases still further.

With reference to FIG. 3, a person skilled in the art will recognizethat the inventive polyethylene composition has a multimodal DSCprofile. For Inventive Example 1 the DSC profile is trimodal.

The data in Table 3, clearly shows that in contrast to each of thecomparative resins, the inventive polyethylene composition has asignificantly lower CDBI₅₀ as obtained from a crystallization elutionfractionation (CEF) analysis. Inventive Example 1 has CDBI₅₀ of lessthan 45 weight percent (Inventive Example 1, is 22.2 weight percent;while all of the Comparative Examples 1-9, have CDBI₅₀ values obtainedfrom a crystallization elution fractionation (CEF) analysis of greaterthan 45 weight percent).

Blown films were generated by using a 2.5-inch Gloucester blown filmline (L/D=24) with a die diameter of 4-inch. The die was coated withpolymer processing aid (PPA) by spiking the line with a highconcentration of PPA masterbatch to avoid melt fracture. The fixedconditions were die gap of 35 mils (0.0889 cm), frost line height ofabout 17 inches and output of 100 lbs/hr. Films were collected underdifferent orientation conditions. The monolayer 1-mil film was producedwith a blow up ratio (BUR) of 2.5 and the 1-mil films were used forobtaining the physical properties of the films. The monolayer 2-mil film(BUR=2.5) was used for obtaining the cold-seal and hot tack profiles.Data for film blown from the polyethylene compositions of the presentdisclosure is provided in Table 5, along with data for films made fromvarious comparative resins.

Comparative Example 1 is a film made from ELITE® 5400G, a resincommercially available from the Dow Chemical Company. ELITE 5400G has adensity of about 0.916 g/cm³ and a melt index I₂ of about 1 dg/min.Comparative Example 2 is a film made from SURPASS® FP117-C, a resincommercially available from the NOVA Chemicals Corporation. SURPASSFP117-C has a density of 0.917 g/cm³ and a melt index I₂ of 1 dg/min.Comparative Examples 3 and 4 are films made from resins made accordingto US Pat. Appl. Pub. No. 2016/0108221. Comparative

Example 3 is a film made from an ethylene/1-octene copolymer which has adensity of about 0.917 g/cm³, a melt index I₂ of about 0.96 dg/min, andwhich was made in a multi reactor solution process in which a firstreactor and a second reactor are configured in series with one another.Comparative Example 4 is a film made from an ethylene/1-octene copolymerwhich has a density of about 0.913 g/cm³, a melt index I₂ of about 0.85dg/min, and which was made in a multi reactor solution process in whicha first reactor and a second reactor are configured in series with oneanother. Comparative Example 5 is a film made from SCLAIR® FP112-A, aresin commercially available from the NOVA Chemicals Corporation.SCLAIR® FP112-A has a density of 0.912 g/cm³ and a melt index I₂ of 0.9dg/min. Comparative Example 6 is a film made from EXCEED® 1018CA, aresin commercially available from ExxonMobil. EXCEED® 1018CA has adensity of about 0.918 g/cm³ and a melt index I₂ of about 0.94 dg/min.Comparative Example 7 is a film made from MARLEX® D139, a resincommercially available from ChevronPhillips. MARLEX® D139 has a densityof about 0.918 g/cm³ and a melt index I₂ of about 0.9 dg/min.Comparative Example 8 is a film made from SCLAIR® FP120-A, a resincommercially available the NOVA Chemicals Corporation. FP120-A has adensity of 0.920 g/cm³ and a melt index I₂ of 1 dg/min. ComparativeExample 9 is a film made from SCLAIR® FP026-F, a resin commerciallyavailable the NOVA Chemicals Corporation. FP026-F has a density of 0.926g/cm³ and a melt index I₂ of 0.75 dg/min. In Table 5, the InventiveExample 1 is a film made from the Inventive polyethylene composition ofInventive Example 1.

TABLE 5 Film Properties Inventive PE Example No. Composition 1Comparative 1 Comparative 2 Comparative 3 Film Physical PropertiesThickness Profile Ave 1.03 1.03 1.01 1.04 Film Toughness Dart Impact(g/mil) 461 818 470 812 Slow Puncture - Lube/Tef 42 63 85 98 (J/mm) ASTMPuncture (J/mm) 93 97 66 Film Tear Resistance Tear - MD (g/mil) 413 247308 293 Tear - TD (g/mil) 560 485 516 540 Film Stiffness 1% SecModulus - MD 236 165 129 150.4 (Mpa) 1% Sec Modulus - TD 263.4 175 131.4167.8 (Mpa) 2% Sec Modulus - MD 216.8 151 117 141.4 (Mpa) 2% SecModulus - TD 241.4 155 123.8 149.2 (Mpa) Film Tensile Strength TensileBreak Str - MD 56.7 44 46.4 45.4 (Mpa) Tensile Break Str - TD 48 45.5 4844.6 (Mpa) Elongation at Break - MD 663 486 534 521 (%) Elongation atBreak - TD 815 725 796 747 (%) Tensile Yield Str - MD 11 9.1 8.8 9.1(Mpa) Tensile Yield Str - TD 12.2 8.7 8.8 8.9 (Mpa) Tensile Elong atYield - 10 13 22 13 MD (%) Tensile Elong at Yield - 10 13 17 14 TD (%)Film Opticals Gloss at 45° 51 64 50 72 Haze (%) 10.8 7.8 12 5.8 ColdSeal Properties S.I.T. @ 8.8 N Seal 75.3 100.4 98.8 98.2 Strength (° C.)Max Force (N) 24.45 24.9 19.9 23.7 Temp. @ Max Force (° C.) 165 150 130160 Hot Tack Properties Tack Onset @ 1.0 N (° C.) - 68.15 92.5 100.595.4 2 mil film Max Hottack Strength (N) - 5.45 5.4 4.1 4.4 2 mil filmTemperature - Max. 107.5 110 115 115 Hottack (° C.) - 2 mil film AHTW(Newtons · ° C.) 261 140 95.3 111 OTR (cm³ per 100 inch²) 715.6 — 662.8704.6 Example No. Comparative 4 Comparative 5 Comparative 6 Comparative7Film Physical Properties Thickness Profile Ave 1 1 1.01 1.03 FilmToughness Dart Impact (g/mil) 891 546 827 688 Slow Puncture - Lube/Tef80 77 (J/mm) ASTM Puncture (J/mm) 151 84 Film Tear Resistance Tear - MD(g/mil) 231 376 241 186 Tear - TD (g/mil) 548 580 358 454 Film Stiffness1% Sec Modulus - MD 145 113 156.8 177.6 (Mpa) 1% Sec Modulus - TD 134111 168.8 185 (Mpa) 2% Sec Modulus - MD 149 136 150.2 166.4 (Mpa) 2% SecModulus - TD 136 127 161.4 170.2 (Mpa) Film Tensile Strength TensileBreak Str - MD 51.8 56.4 50.7 47.8 (Mpa) Tensile Break Str - TD 50.653.5 61.1 47.8 (Mpa) Elongation at Break - MD 557 479 566 505 (%)Elongation at Break - TD 751 761 741 692 (%) Tensile Yield Str - MD 7.98 9.7 10.1 (Mpa) Tensile Yield Str - TD 7.6 7.7 9.9 9.2 (Mpa) TensileElong at Yield - 10 16 15 16 MD (%) Tensile Elong at Yield - 10 15 14 12TD (%) Film Opticals Gloss at 45° 83.8 67 39 84 Haze (%) 2.9 6.8 16.23.3 Cold Seal Properties S.I.T. @ 8.8 N Seal 93.5 89.75 102.8 102.4Strength (° C.) Max Force (N) 24.4 24.70 20.6 23.4 Temp. @ Max Force (°C.) 160 155 140 120 Hot Tack Properties Tack Onset @ 1.0 N (° C.) - 8778 101.2 98.6 2 mil film Max Hottack Strength (N) - 5.1 3.5 5.3 5.7 2mil film Temperature - Max. 105 120 120 120 Hottack (° C.) - 2 mil filmAHTW (Newtons · ° C.) 151 114 103 103.5 OTR (cm³ per 100 inch²) 771.5845 552.2 545.1 Example. No. Comparative 8 Comparative 9 Film PhysicalProperties Thickness Profile Ave 1 1 (mil) Film Toughness Dart Impact(g/mil) 214 156 Slow Puncture - Lube/Tef 73 25 (J/mm) ASTM Puncture(J/mm) 78.5 78 Film Tear Resistance Tear - MD (g/mil) 384 295 Tear - TD(g/mil) 616 640 Film Stiffness 1% Sec Modulus - MD 193 243 (Mpa) 1% SecModulus - TD 197 252 (Mpa) 2% Sec Modulus - MD 176 213 (Mpa) 2% SecModulus - TD 179 220 (Mpa) Film Tensile Strength Tensile Break Str - MD52.6 38.4 (Mpa) Tensile Break Str - TD 42.8 35.8 (Mpa) Elongation atBreak - MD 608 707 (%) Elongation at Break - TD 767 729 (%) TensileYield Str - MD 10.4 12.7 (Mpa) Tensile Yield Str - TD 10.4 13.2 (Mpa)Tensile Elong at Yield - 10.2 10.5 MD (%) Tensile Elong at Yield - 10.713.2 TD (%) Film Opticals Gloss at 45° 61.7 56 Haze (%) 11.8 14.0 ColdSeal Properties S.I.T. @ 8.8 N Seal 107.5 116.0 Strength (° C.) MaxForce (N) 26.5 31.9 Temp. @ Max Force (° C.) 150 180 Hot Tack PropertiesTack Onset @ 1.0 N (° C.) - 98.75 106.4 2 mil film Max Hottack Strength(N) - 4.16 4.3 2 mil film Temperature - Max. 120 140 Hottack (° C.) - 2mil film AHTW (Newtons · ° C.) 139.1 28.4 OTR (cm³ per 100 inch²) 650.8382.4

The data provided in Table 5 together with the data in FIGS. 4-8demonstrate that the inventive polyethylene composition can be made intoa film having a good balance of properties, including good stiffness,good oxygen transmission rates and good sealing properties. For example,and with reference to FIGS. 4-8, the film made from the inventivepolyethylene composition has good hot tack and cold seal performance.

Without wishing to be bound by theory, in the hot tack (or cold seal)profile (seal temperature vs. seal force), good hot tack (or cold seal)performance is indicated by an early (or low) hot tack (or cold seal)initiation temperature, then a relatively high sealing force over a widerange of hot tack seal temperatures. See for example the shape thecurves in FIGS. 4 and 5 for Inventive Example 1, relative to ComparativeExamples 1-7. The shape of the hot tack curves for Inventive Example 1,is particularly good and has an early hot tack seal initiationtemperature combined by a high sealing force over a wide range of hottack seal temperatures. In an effort to provide a more quantitativelymeasurement of this improved hot tack sealing performance, a newparameter, the “area of the hot-tack (strength) window” (the “area ofhot tack window” or the “AHTW”) has been defined herein. The AHTW issimply an estimate of the area under the hot tack curve from thehot-tack on-set temperature to the temperature immediately prior to themelting of the specimen. As shown in FIG. 4, the temperature prior tothe melting of the specimen was typically at 130° C., but notnecessarily at 130° C. As shown in Table 5 and in FIG. 4, the InventiveExample 1 has an AHTW of greater than 220 Newtons·° C., whereas each ofthe Comparative Examples, 1-7, have an AHTW of less than 160 Newtons·°C.

Good cold seal properties are evidenced by the curves given in FIG. 5for the Inventive Example 1. For comparison, the cold seal properties ofComparative Examples 1-7 are also shown in FIG. 5. From FIG. 5, a personskilled in the art will recognize that the Inventive Example 1 has anearly cold seal initiation temperature in combination with a relativelyhigh seal force over a wide range of cold seal temperatures. Incontrast, the Comparative Examples, 1-7 have a later cold sealinitiation temperature, with a narrower range of cold seal temperaturesover which a relatively high seal force occurs.

FIG. 6 shows that the Inventive Example 1, has a better balance of AHTWand stiffness (as determined by the machine direction (MD) secantmodulus at 1 strain) than do the Comparative Examples 2-9. Indeed, FIG.6, which plots the AHTW (in Newtons·° C.) values (the y-axis) againstthe machine direction (MD) secant modulus at 1% strain (in MPa) values(the x-axis), along with plot of the equation: AHTW=−2.0981 (machinedirection (MD) 1% secant modulus)+564.28, shows that the InventiveExample 1 satisfies the condition: AHTW>−2.0981 (machine direction (MD)1% secant modulus)+564.28, whereas the Comparative Examples 2-9 do not.

FIG. 7, shows that the Inventive Example, has a better balance of SITand stiffness (as determined by the machine direction (MD) secantmodulus at 1% strain) than do the Comparative Examples 2-9. FIG. 7,which plots the SIT (in ° C.) values (the y-axis) against the machinedirection (MD) secant modulus at 1% strain (in MPa) values (the x-axis),along with plot of the equation: SIT=0.366 (machine direction (MD) 1%secant modulus)+22.509, shows that the Inventive Example 1 satisfies thecondition: SIT<0.366 (machine direction (MD) 1% secant modulus)+22.509,whereas the Comparative Examples 2-9 do not.

FIG. 8, shows that the Inventive Example 1, has a better balance of OTRand stiffness (as determined by the machine direction (MD) secantmodulus at 1% strain) than do the Comparative Examples 2-9. FIG. 8,which plots the OTR (in cm³ per 100 inch²) values (the y-axis) againstthe machine direction (MD) secant modulus at 1% strain (in MPa) values(the x-axis), along with plot of the equation: OTR=−5.4297 (machinedirection (MD) 1% secant modulus)+1767.8, shows that the InventiveExample 1 satisfies the condition: OTR>−5.4297 (machine direction (MD)1% secant modulus)+1767.8, whereas the Comparative Examples 2-9 do not.

Non-limiting embodiments of the present disclosure include thefollowing:

Embodiment A. A polyethylene composition including:

from 15 to 80 wt % of a first polyethylene which is an ethylenecopolymer, the first polyethylene having a weight average molecularweight Mw of from 70,000 to 250,000, a molecular weight distributionM_(w)/M_(n) of <2.3 and from 5 to 100 short chain branches per thousandcarbon atoms;

from 5 to 50 wt % of a second polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight, Mw of from 50,000 to 200,000, amolecular weight distribution M_(w)/M_(n) of <2.3 and from 0 to 15 shortchain branches per thousand carbon atoms; and

from 5 to 50 wt % of a third polyethylene which is an ethylene copolymeror an ethylene homopolymer, the third polyethylene having a weightaverage molecular weight, Mw of from 70,000 to 200,000, a molecularweight distribution M_(w)/M_(n) of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms; wherein

the number of short chain branches per thousand carbon atoms in firstpolyethylene (SCB_(PE-1)) is greater than the number of short chainbranches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)) and the third polyethylene (SCB_(PE-3)); and

the polyethylene composition has a density of 0.939 g/cm³, a melt indexI₂ of from 0.1 to 10 g/10min, and a composition distribution breadthindex CDBI₅₀ obtained from a crystallization elution fractionation (CEF)analysis of <45 wt %.

Embodiment B. The polyethylene composition of Embodiment A wherein theweight average molecular weight of the second polyethylene is less thanthe weight average molecular weight of the first polyethylene.

Embodiment C. The polyethylene composition of Embodiment A or B whereinthe weight average molecular weight of the second polyethylene is lessthan the weight average molecular weight of the third polyethylene.

Embodiment D. The polyethylene composition of Embodiment A, B or Cwherein the number of short chain branches per thousand carbon atoms inthe third polyethylene (SCB_(PE-3)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)).

Embodiment E. The polyethylene composition of Embodiment A, B, C or Dwherein the polyethylene composition has composition distributionbreadth index CDBI₅₀ obtained from a crystallization elutionfractionation (CEF) analysis of <35 wt %.

Embodiment F. The polyethylene composition of Embodiment A, B, C, D or Ewherein the polyethylene composition has a unimodal profile in a gelpermeation chromatograph (GPC).

Embodiment G. The polyethylene composition of Embodiment A, B, C, D, Eor F wherein the polyethylene composition has a melting peak temperaturein a differential scanning calorimetry (DSC) analysis at above 125° C.

Embodiment H. The polyethylene composition of Embodiment A, B, C, D, E,F or G wherein the polyethylene composition has a melting peaktemperature in a differential scanning calorimetry (DSC) analysis atbelow 90 ° C.

Embodiment I. The polyethylene composition of Embodiment A, B, C, D, E,F, G or H wherein the polyethylene composition has three melting peaksin a differential scanning calorimetry (DSC) analysis.

Embodiment J. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H or I wherein the first polyethylene has from 15 to 50 shortchain branches per thousand carbon atoms.

Embodiment K. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I or J wherein the second polyethylene is an ethylenehomopolymer.

Embodiment L. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J or K wherein the third polyethylene is an ethylenecopolymer and has from 0.1 to 5 short chain branches per thousand carbonatoms.

Embodiment M. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K or L wherein the first polyethylene has a weightaverage molecular weight, Mw of from 75,000 to 175,000.

Embodiment N. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L or M wherein the second polyethylene has a weightaverage molecular weight, Mw of from 60,000 to 150,000.

Embodiment O. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M or N wherein the third polyethylene has a weightaverage molecular weight, Mw of from 75,000 to 175,000.

Embodiment P. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N or O wherein the first polyethylene has adensity of from 0.860 to 0.916 g/cm³.

Embodiment Q. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O or P wherein the second polyethylene is anethylene homopolymer having a density of from 0.930 to 0.980 g/cm³.

Embodiment R. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P or Q wherein the third polyethylene isan ethylene copolymer having a density of from 0.916 to 0.980 g/cm³.

Embodiment S. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q or R wherein the first polyethyleneis present in from 35 to 75 wt %.

Embodiment T. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R or S wherein the secondpolyethylene is present in from 15 to 40 wt %.

Embodiment U. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S or T wherein the thirdpolyethylene is present in from 10 to 35 wt %.

Embodiment V. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T or U wherein the firstpolyethylene has a CDBI₅₀ of at least 75 wt %.

Embodiment W. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U or V wherein the thirdpolyethylene is a copolymer with a CDBI₅₀ of at least 75 wt %.

Embodiment X. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V or W wherein the firstpolyethylene is a homogeneously branched ethylene copolymer.

Embodiment Y. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W or X wherein thethird polyethylene is a homogeneously branched ethylene copolymer.

Embodiment Z. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X or Y wherein thefirst polyethylene is a made with a single site catalyst.

Embodiment AA. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y or Z whereinthe second polyethylene is made with a single site catalyst.

Embodiment BB. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z or AAwherein the third polyethylene is made with a single site catalyst.

Embodiment CC. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA or BBwherein the polyethylene composition has a molecular weight distributionM_(w)/M_(n) of <2.5.

Embodiment DD. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA or BBwherein the polyethylene composition has a molecular weight distributionM_(w)/M_(n) of from 1.5 to 3.5.

Embodiment EE. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB,CC or DD wherein the polyethylene composition has a density of <0.935g/cm³.

Embodiment FF. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB,CC or DD wherein the polyethylene composition has a density of from0.880 to 0.932 g/cm³.

Embodiment GG. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB,CC, DD, EE or FF wherein the polyethylene composition has a melt index,I₂ of from 0.1 to 3.0 dg/min.

Embodiment HH. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB,CC, DD, EE, FF or GG wherein the polyethylene composition has a Mz/M_(w)of less than 2.3.

Embodiment II. The polyethylene composition of Embodiment A, B, C, D, E,F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB,CC, DD, EE, FF, GG or HH wherein the polyethylene composition has a meltindex ratio, I₂₁/I₂ of from 15 to 40.

Embodiment JJ. A film layer having a thickness of from 0.5 to 10 mil,including the polyethylene composition of Embodiment A, B, C, D, E, F,G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC,DD, EE, FF, GG, HH or II.

Embodiment KK. The film layer of Embodiment JJ wherein the film layerhas a machine direction (MD) 1% secant modulus of ≥220 MPa when measuredat a film thickness of about 1 mil.

Embodiment LL. The film layer of Embodiment JJ or KK wherein the filmlayer has a dart impact strength of ≥400 g/mil.

Embodiment MM. The film layer of Embodiment JJ, KK or LL wherein thefilm layer has a machine direction (MD) tear strength of ≥400 g/mil.

Embodiment NN. The film layer of Embodiment JJ wherein the film layerhas a machine direction (MD) 1% secant modulus of ≥200 MPa when measuredat a film thickness of about 1 mil; a dart impact strength of ≥400 g/miland a machine direction (MD) tear strength of ≥400 g/mil.

Embodiment OO. The film layer of Embodiment JJ, KK, LL, MM or NN whereinthe film layer has a seal initiation temperature (SIT) of ≤85° C. whenmeasured at a film thickness of about 2 mil.

Embodiment PP. The film layer of Embodiment JJ, KK, LL, MM, NN or OOwherein the film layer has an area of hot tack window (AHTW) of ≥220Newtons·° C. when measured at a film thickness of about 2 mil.

Embodiment QQ. The film layer of Embodiment JJ, KK, LL, MM, NN, OO or PPwherein the film layer has an oxygen transmission rate (OTR) of ≥600 cm³per 100 inch² when measured at a film thickness of about 1 mil.Embodiment RR. The film layer of Embodiment JJ wherein the film layerhas a machine direction (MD) 1% secant modulus of ≥200 MPa when measuredat a film thickness of about 1 mil, a seal initiation temperature (SIT)of ≤85° C. when measured at a film thickness of about 2 mil, an area ofhot tack window (AHTW) of 220 Newtons·° C. when measured at a filmthickness of about 2 mil, and an oxygen transmission rate (OTR) of ≥600cm³ per 100 inch² when measured at a film thickness of about 1 mil.

Embodiment SS. A film layer having a thickness of from 0.5 to 10 mil,wherein the film layer has a machine direction (MD) 1% secant modulus of≥200 MPa when measured at a film thickness of about 1 mil and a sealinitiation temperature (SIT) of ≤85° C. when measured at a filmthickness of about 2 mil.

Embodiment TT. A film layer having a thickness of from 0.5 to 10 mil,wherein the film layer has a has a machine direction (MD) 1% secantmodulus of ≥200 MPa when measured at a film thickness of about 1 mil andan area of hot tack window (AHTW) of ≥220 Newtons·° C. when measured ata film thickness of about 2 mil.

Embodiment UU. A film layer having a thickness of from 0.5 to 10 mil,wherein the film layer has a has a machine direction (MD) 1% secantmodulus of ≥200 MPa when measured at a film thickness of about 1 mil andan oxygen transmission rate (OTR) of ≥600 cm³ per 100 inch² whenmeasured at a film thickness of about 1 mil.

Embodiment VV. A film layer having a thickness of from 0.5 to 10 mil,wherein the film layer has a has a machine direction (MD) 1% secantmodulus of ≥200 MPa when measured at a film thickness of about 1 mil, anoxygen transmission rate (OTR) of ≥600 cm³ per 100 inch² when measuredat a film thickness of about 1 mil, a seal initiation temperature (SIT)of ≤85° C. when measured at a film thickness of about 2 mil, and an areaof hot tack window (AHTW) of ≥220 Newtons·° C. when measured at a filmthickness of about 2 mil.

Embodiment WW. A film layer having a thickness of from 0.5 to 10 mil,wherein the film layer has a has a machine direction (MD) 1% secantmodulus of ≥200 MPa when measured at a film thickness of about 1 mil, anoxygen transmission rate (OTR) of ≥600 cm³ per 100 inch² when measuredat a film thickness of about 1 mil, a seal initiation temperature (SIT)of ≤85° C. when measured at a film thickness of about 2 mil, an area ofhot tack window (AHTW) of ≥220 Newtons·° C. when measured at a filmthickness of about 2 mil, a dart impact strength of ≥400 g/mil and amachine direction (MD) tear strength of ≥400 g/mil.

Embodiment XX. Film including the polyethylene composition of EmbodimentA, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X,Y, Z, AA, BB, CC, DD, EE, FF, GG, HH or II, the film satisfying thefollowing relationship:

area of hot tack window (AHTW)>−2.0981 (machine direction (MD) 1% secantmodulus)+564.28;

wherein the AHTW is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

Embodiment YY. Film including the polyethylene composition of EmbodimentA, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X,Y, Z, AA, BB, CC, DD, EE, FF, GG, HH or II, the film satisfying thefollowing relationship: oxygen transmission rate (OTR)>−5.4297 (machinedirection (MD) 1% secant modulus)+1767.8;

wherein the OTR is measured at a film thickness of about 1 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

Embodiment ZZ. Film including the polyethylene composition of EmbodimentA, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X,Y, Z, AA, BB, CC, DD, EE, FF, GG, HH or II, the film satisfying thefollowing relationship:

seal initiation temperature (SIT)<0.366 (machine direction (MD) 1%secant modulus)+22.509;

wherein the SIT is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

Embodiment AAA. Film including the polyethylene composition ofEmbodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T,U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF, GG, HH or II, the filmsatisfying the following relationships:

i) area of hot tack window (AHTW)>−2.0981 (machine direction (MD) 1secant modulus)+564.28;

wherein the AHTW is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil;

ii) oxygen transmission rate (OTR)>−5.4297 (machine direction (MD) 1%secant modulus)+1767.8;

wherein the OTR is measured at a film thickness of about 1 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil; and

iii) seal initiation temperature (SIT)<0.366 (machine direction (MD) 1%secant modulus)+22.509;

wherein the SIT is measured at a film thickness of about 2 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

What is claimed is:
 1. A polyethylene composition which when made into afilm layer having a thickness of about 1 mil exhibits a machinedirection (MD) 1% secant modulus of ≥200 MPa and oxygen transmissionrate (OTR) of ≥600 cm³ per 100 inch² per day, and when made into a filmlayer having a thickness of about 2 mil exhibits a seal initiationtemperature (SIT) of ≤85° C., and an area of hot tack window (AHTW) of≥220 Newtons·° C.
 2. The polyethylene composition of claim 1, whereinthe 1 mil film exhibits a MD 1% secant modulus of ≥210 MPa.
 3. Thepolyethylene composition of claim 1, wherein the 1 mil film exhibits aMD 1% secant modulus of ≥230 MPa.
 4. The polyethylene composition ofclaim 1, wherein the 1 mil film exhibits a MD 1% secant modulus of 200MPa to 270 MPa.
 5. The polyethylene composition of claim 1, wherein the1 mil film exhibits an oxygen transmission rate (OTR) of ≥650 cm³ per100 inch².
 6. The polyethylene composition of claim 1, wherein the 1 milfilm exhibits an oxygen transmission rate (OTR) of ≥700 cm³ per 100inch².
 7. The polyethylene composition of claim 1, wherein the 1 milfilm exhibits an oxygen transmission rate (OTR) of from 600 to 800 cm³per 100 inch².
 8. The polyethylene composition of claim 1, wherein the 1mil film exhibits an oxygen transmission rate (OTR) of from 650 to 750cm³ per 100 inch².
 9. The polyethylene composition of claim 1, whereinthe film layer having a thickness of about 2 mil exhibits a SIT of 70°C. to 80° C.
 10. The polyethylene composition of claim 1, wherein thefilm layer having a thickness of about 2 mil exhibits a AHTW of 220 to290 Newtons·° C.
 11. A polyethylene composition which when made into afilm layer having a thickness of about 1 mil exhibits a machinedirection (MD) 1% secant modulus of ≥200 MPa, an oxygen transmissionrate (OTR) of ≥600 cm³ per 100 inch² per day, a dart impact strength of≥400 g/mil and a machine direction (MD) tear strength of ≥400 g/mil, andwhen made into a film layer having a thickness of about 2 mil exhibits aseal initiation temperature (SIT) of ≤85° C., and an area of hot tackwindow (AHTW) of ≥220 Newtons·° C.
 12. The polyethylene composition ofclaim 11, wherein the 1 mil film exhibits a MD 1% secant modulus of ≥210MPa.
 13. The polyethylene composition of claim 11, wherein the 1 milfilm exhibits a MD 1% secant modulus of 200 MPa to 270 MPa.
 14. Thepolyethylene composition of claim 11, wherein the 1 mil film exhibits adart impact strength of 400 g/mil to 600 g/mil.
 15. The polyethylenecomposition of claim 11, wherein the 1 mil film exhibits an oxygentransmission rate (OTR) of ≥650 cm³ per 100 inch².
 16. The polyethylenecomposition of claim 11, wherein the 1 mil film exhibits an oxygentransmission rate (OTR) of from 600 to 800 cm³ per 100 inch².
 17. Thepolyethylene composition of claim 11, wherein the 1 mil film exhibits anoxygen transmission rate (OTR) of ≥700 cm³ per 100 inch².
 18. Thepolyethylene composition of claim 11, wherein the 1 mil film exhibits atear strength of from 400 g/mil to 450 g/mil.
 19. The polyethylenecomposition of claim 11, wherein the film layer having a thickness ofabout 2 mil exhibits a SIT of 70° C. to 80° C.
 20. The polyethylenecomposition of claim 11, wherein the film layer having a thickness ofabout 2 mil exhibits a AHTW of 220 to 290 Newtons·° C.